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WO2009151109A1 - Polyfluoroalkadiene mixture and method of manufacture therefor - Google Patents

Polyfluoroalkadiene mixture and method of manufacture therefor Download PDF

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Publication number
WO2009151109A1
WO2009151109A1 PCT/JP2009/060731 JP2009060731W WO2009151109A1 WO 2009151109 A1 WO2009151109 A1 WO 2009151109A1 JP 2009060731 W JP2009060731 W JP 2009060731W WO 2009151109 A1 WO2009151109 A1 WO 2009151109A1
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Prior art keywords
reaction
polyfluoroalkadiene
fluorine
mixture
general formula
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PCT/JP2009/060731
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French (fr)
Japanese (ja)
Inventor
勝之 佐藤
清一郎 村田
池田　昭彦
大介 村井
前田　満
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Unimatec Co Ltd
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Unimatec Co Ltd
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Priority to CA2723453A priority Critical patent/CA2723453C/en
Priority to JP2010516889A priority patent/JP5257449B2/en
Priority to CN200980121805.9A priority patent/CN102066296B/en
Priority to EP09762539.6A priority patent/EP2284145B1/en
Priority to US12/993,571 priority patent/US8163857B2/en
Publication of WO2009151109A1 publication Critical patent/WO2009151109A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/20—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/19—Halogenated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/18—Monomers containing fluorine
    • C08F214/182—Monomers containing fluorine not covered by the groups C08F214/20 - C08F214/28

Definitions

  • the present invention relates to a polyfluoroalkadiene mixture and a process for producing the same. More specifically, a compound having a C 6 or less perfluoroalkyl group, polyfluoroalkadiene mixture used as a copolymerizable monomer in the production of the active ingredient is a fluorinated copolymer of the water and oil repellent, etc. And its manufacturing method.
  • Acrylic acid derivatives of perfluoroalkyl alcohol such as CF 3 (CF 2 ) 7 CH 2 CH 2 OCOCH ⁇ CH 2, are used in large quantities as a water / oil repellent synthetic monomer for fibers.
  • perfluoroalkyl alcohol which is a raw material for the acrylate, is widely used as a surfactant or the like (see Patent Document 1).
  • a compound having a perfluoroalkyl group as a structural unit can be applied to the surface of fibers, metals, glass, rubber, resins, etc., thereby improving surface modification, water / oil repellency, antifouling, It is generally known that there is an effect of improving releasability, leveling properties and the like.
  • a C 8 telomer compound is particularly preferred because a compound (telomer compound) having a C 8 to C 12 perfluoroalkyl group is most likely to exhibit the desired performance as described above.
  • telomer compounds having C 8 to C 12 perfluoroalkyl groups in particular have been reported to be biodegraded in the environment and converted to compounds with relatively high bioconcentration and environmental concentration. There are concerns about exposure in the treatment process, waste, release to the environment from the treated substrate, diffusion, and the like. In addition, in the case of a compound having 14 or more carbon atoms in the perfluoroalkyl group, it is very difficult to handle due to its physicochemical properties, and the fact is that it is hardly used.
  • telomer compound having a C 8 or higher perfluoroalkyl group generation or contamination of perfluorooctanoic acids with high bioconcentration properties cannot be avoided in the production process.
  • telomer compounds although promoted the use of alternative to compounds having a withdrawal or C 6 following a perfluoroalkyl group from its production, the carbon number of the perfluoroalkyl group in There 6 the following compounds were significantly reduced in orientation in the treated substrate surface and the melting point, glass transition point or the like is significantly lower than that C 8 compound, temperature, humidity, stress, the use of an organic solvent environment It is greatly influenced by the conditions, and sufficient performance required there is not obtained, and durability is also affected.
  • An object of the present invention is a compound in which the number of continuous CF 2 groups of perfluoroalkyl groups is 5 or less, and is a resinous or elastomeric material that is an active ingredient of a surface treatment agent such as a water / oil repellent and a release agent
  • An object of the present invention is to provide a polyfluoroalkadiene mixture that is effectively used as a copolymerizable monomer in the production of a fluorinated copolymer and a method for producing the same.
  • Such polyfluoroalkadiene mixtures have the general formula CF 3 (CF 2 ) n + 1 CH 2 (CF 2 ) m + 1 (CH 2 CH 2 ) I [II] (Where n is an integer of 0 to 5 and m is an integer of 0 to 6) is reacted with an organic basic compound, and the products [Ia] and [Ib] It is manufactured by obtaining as a mixture fraction.
  • the polyfluoroalkadiene mixture according to the present invention has an unsaturated structure that is easily decomposed into ozonolysis when released into the environment, and is easily decomposed into a compound having low environmental accumulation and bioaccumulation, In addition, environmentally hazardous substances such as perfluoroalkyl carboxylic acids are not generated in the manufacturing process.
  • Such polyfluoroalkadiene mixture of good and that the present invention environmental surfaces, C 8 telomer compared to the surface modification of the C 6 following telomers missing or can not be expressed, water- and oil-repellency, anti It can be effectively used as a copolymerizable monomer for producing a fluorinated copolymer that can improve performance such as soiling, releasability and leveling.
  • the fluorine-containing copolymer obtained by copolymerizing a polyfluoroalkadiene mixture with a fluorinated olefin monomer can be peroxide-crosslinked as a fluorine-containing elastomer.
  • the polyfluoroalkadiene mixture according to the present invention has the general formula CF 3 (CF 2 ) n CH 2 (CF 2 ) m + 1 (CH 2 CH 2 ) I [II] n: 0 to 5 m: 0-6
  • the product [Ia] and [Ib] are produced by reacting an organic basic compound with the polyfluoroalkyl iodide represented by the formula ( II) and dehydrating it, and deHFing the —CF 2 CH 2 CF 2 — bond. ] As a mixture.
  • the compound [Ia] and [Ib] formed as a mixture are bonded to the H atom of the methylene chain CH 2 and the front and back positions in the deHF reaction carried out together with the deHI reaction. This is because extraction with any one F atom of the fluoromethylene chain CF 2 occurs equivalently before and after. Further, since the resulting polyfluoroalkadiene mixture is equivalent to the deHF reaction, the production ratio of the products [Ia] and [Ib] is almost halved. Since these products [Ia] and [Ib] are very similar structural isomers, they cannot be separated and identified, but they have the same reactivity, so that they remain as a mixture. It can be used as a raw material for the synthesis of
  • Polyfluoroalkyl iodide can be obtained by addition reaction of terminally iodized polyfluoroalkane with ethylene.
  • the terminal iodinated polyfluoroalkane include the following compounds. CF 3 (CF 2 ) (CH 2 CF 2 ) I CF 3 (CF 2 ) 2 (CH 2 CF 2 ) I CF 3 (CF 2 ) 3 (CH 2 CF 2 ) I CF 3 (CF 2 ) 4 (CH 2 CF 2 ) I CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) I CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) 2 I CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) 2 I CF 3 (CF 2 ) 2 (CH 2 CF 2 ) (CF 2 CF 2 ) I CF 3 (CF 2 ) 2 (CH 2 CF 2 ) (CF 2 CF
  • the addition reaction of ethylene is carried out by subjecting the above compound [A] to addition reaction of pressurized ethylene in the presence of a peroxide initiator.
  • the number of additions depends on the reaction conditions, but it is 1 or more, preferably 1 It is.
  • the reaction temperature is related to the decomposition temperature of the initiator used, the reaction is generally carried out at about 80 to 120 ° C. When a peroxide initiator that decomposes at a low temperature is used, the reaction temperature is 80 ° C. or less. Reaction is possible.
  • tertiary butyl peroxide di (tertiary butyl cyclohexyl) peroxydicarbonate, dicetyl peroxydicarbonate and the like are used in an amount of about 1 to 5 mol% with respect to the compound [A]. Used in proportions.
  • organic basic compounds include nitrogen-containing organic basic compounds such as diethylamine, triethylamine, pyridine or derivatives thereof, diethanolamine, triethanolamine, 1,8-diazabicyclo [5.4.0] -7-undecene, diazabicyclononene, etc.
  • Monovalent metal alkoxides such as sodium methoxide, sodium ethoxide and potassium methoxide, preferably nitrogen-containing organic basic compounds with low nucleophilicity, particularly preferably 1,8-diazabicyclo [5.4.0]- 7-Undecene is used.
  • organic basic compounds are used in a molar ratio of about 0.1 to 10, preferably 0.95 to 3.5, more preferably 1.95 to 2.5 with respect to polyfluoroalkane iodide [II].
  • 1,8-diazabicyclo [5.4.0] -7-undecene is used in a fluorine-containing organic solvent at a preferred molar ratio of 1.95 to 2.5, or when triethylamine is used in a tetrahydrofuran solvent.
  • the dehydrohalogenation reaction is carried out without a solvent, but is preferably carried out in the presence of water or an organic solvent from the viewpoint of reaction efficiency and heat generation control.
  • organic solvent include alcohols such as methanol, ethanol, propanol and isopropanol, ethers such as diethyl ether, 1,4-dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and aromatics such as toluene and cyclohexane.
  • Aprotic such as aromatic or alicyclic hydrocarbons, acetonitrile, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone Polar solvents, hydrochlorofluorocarbons such as HCFC-225, and fluorine-containing organic solvents such as hydrofluoroethers (for example, 3M product Novec HFE) are used.
  • hydrofluorocarbons such as HCFC-225
  • fluorine-containing organic solvents such as hydrofluoroethers (for example, 3M product Novec HFE) are used.
  • Water or an organic solvent is used in a volume ratio of about 0.1 to 100, preferably about 1 to 10, and more preferably 3 to 6 with respect to the polyfluoroalkane iodide [II].
  • the reaction efficiency is not affected even if the amount of the solvent is increased, it is preferably used in a volume ratio of 3 to 6.
  • the dehydrohalogenation reaction is performed at about -20 to 100 ° C, preferably about -10 to 80 ° C. At temperatures higher than this, side reactions proceed and a large amount of by-products with unknown structures are generated.
  • the reaction pressure may be any of reduced pressure, atmospheric pressure, and pressurized pressure, and it is preferable to carry out the reaction at atmospheric pressure for the convenience of the reaction apparatus.
  • the target polyfluoroalkadiene mixture Can be obtained.
  • the stationary phase separation is not performed by using a polar solvent, for example, the solvent is distilled off under reduced pressure and then the same treatment as in the case of stationary phase separation is performed.
  • X H, F Y: H, F, C n F 2n + 1 (n: 1 to 3), O [CF (Z) CF 2 O] m C n F 2n + 1 (Z: F, CF 3 , n: 1 to 3 , M: 0-5)
  • X and Y are the same or different, and at least one of them is an F atom or a fluorine-containing group.
  • fluorinated olefin monomer represented by the above general formula in which the polyfluoroalkadiene mixture is copolymerized examples include vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, and lower alkyl perfluorocarbons having 1 to 3 carbon atoms.
  • vinylidene fluoride tetrafluoroethylene
  • hexafluoropropylene hexafluoropropylene
  • lower alkyl perfluorocarbons having 1 to 3 carbon atoms.
  • CF 2 CFO [CF (CF 3 ) CF 2 O] n CF 3 (n: 1 to 5)
  • the proportion is about 1.5 mol% or less, preferably about 0.02 to 0.5 mol% (about 5 wt% or less, preferably about 0.1 to 2 wt% based on the total amount of charged monomers).
  • the polyfluoroalkadiene mixture to be copolymerized is a bifunctional monomer having two types of unsaturated bonds, each having different reactivity, and is a fluorine-containing elastomer or polyfluoroalkadiene that does not copolymerize polyfluoroalkadiene.
  • CF 2 CF [OCF 2 CF (CF 3 )] m OCF 2 CF 2 O [CF (CF 3 ) CF 2 O]
  • n CF CF 2 (where m + n is 0-8)
  • a fluorine-containing elastomer copolymerized with another bifunctional monomer represented by (an integer) a crosslinked fluorine-containing elastomer having excellent vulcanization properties and compression set resistance can be provided. .
  • a bromine group-containing or iodine group-containing unsaturated monomer compound, preferably a bromine group-containing unsaturated monomer compound, together with such a polyfluoroalkadiene mixture is contained in the fluoroelastomer in an amount of about 5 mol% or less, preferably about 1 mol%.
  • the crosslinking properties of the fluoroelastomer obtained by the copolymerization specifically, elongation at break, strength at break, resistance to compression set, and the like can be further improved.
  • bromine group-containing unsaturated monomer compounds examples include vinyl bromide, 2-bromo-1,1-difluoroethylene, perfluoroallyl bromide, 4-bromo-1,1,2-trifluorobutene-1, 4 -Bromo-3,3,4,4-tetrafluorobutene-1, 4-bromo-1,1,3,3,4,4-hexafluorobutene-1, bromotrifluoroethylene, 4-bromo-3- Chloro-1,1,3,4,4-pentafluorobutene-1, 6-bromo-5,5,6,6-tetrafluorohexene-1, 4-bromoperfluorobutene-1, 3,3-difluoro
  • a brominated vinyl compound such as allyl bromide or a brominated olefin can be used, but a bromine group-containing vinyl ether represented by the following general formula is preferably used.
  • BrRf-O-CF CF 2 BrRf: bromine group-containing perfluoroalkyl group
  • iodine-containing unsaturated monomer compound iodotrifluoroethylene, 1,1-difluoro-2-iodoethylene, perfluoro (2-iodoethyl vinyl ether), vinyl iodide, or the like is used.
  • R (Br) n (I) m (wherein R is a saturated fluorohydrocarbon having 2 to 6 carbon atoms) Or a saturated chlorofluorohydrocarbon group, n, m is 0.1 or 2, and m + n is 2) in the presence of these compounds.
  • a copolymerization reaction of polyfluoroalkadiene and other fluorinated olefin monomers can be carried out.
  • these compounds act as chain transfer agents and serve to regulate the molecular weight of the resulting fluorinated copolymer, and as a result of the chain transfer reaction, bromine and / or A fluorine-containing copolymer having iodine atoms bonded thereto is obtained, and these sites form cured sites.
  • a chain transfer agent a known iodide represented by the general formula IC n F 2n I, such as a halide represented by I (CF 2 ) 4 I or a general formula IC n F 2n Br, such as IC (CF 2 ), for example.
  • IC n F 2n I such as a halide represented by I (CF 2 ) 4 I
  • IC n F 2n Br such as IC (CF 2 )
  • the copolymerization reaction is performed by an aqueous emulsion polymerization method or an aqueous suspension polymerization method.
  • a water-soluble peroxide alone or a redox system in combination with a water-soluble reducing substance can be used as a reaction initiator system.
  • water-soluble peroxides include ammonium persulfate, potassium persulfate, and sodium persulfate.
  • water-soluble reducing substances include sodium sulfite and sodium bisulfite.
  • a pH regulator such as sodium monohydrogen phosphate, sodium dihydrogen phosphate, potassium monohydrogen phosphate, potassium dihydrogen phosphate, etc. is also used as a stabilizer for the produced aqueous emulsion. .
  • the emulsion polymerization reaction has the general formula RfCOOM
  • Rf Fluoroalkyl group Perfluoroalkyl group Fluorooxyalkyl group Perfluorooxyalkyl group, etc.
  • M Performed in the presence of an ammonium salt or an emulsifier represented by an alkali metal.
  • the amount of the emulsifier used is about 0.1 to 20% by weight, preferably about 0.2 to 2% by weight, based on water.
  • the molecular weight can be adjusted by adjusting the relationship between the copolymerization rate and the initiator amount.
  • chain transfer agents such as C 4 to C 6 hydrocarbons, alcohols, ethers, esters, It can also be easily carried out by using ketones, organic halides and the like.
  • reaction temperature and reaction pressure vary depending on the decomposition temperature of the initiator used and the copolymer composition required, but in order to obtain an elastomeric copolymer, about 0 to 100 ° C., preferably about Reaction conditions of 40-80 ° C., about 0.8-4.5 MPa ⁇ G, preferably about 0.8-4.2 MPa ⁇ G are generally used.
  • the fluorine-containing elastomer obtained in this way has iodine or the like derived from a fluoroolefin iodide mixture that acts as a peroxide crosslinkable group in the copolymer, and is thus peroxide crosslinked by an organic peroxide.
  • organic peroxide used for peroxide crosslinking include 2,5-dimethyl-2,5-bis (tertiary butylperoxy) hexane, 2,5-dimethyl-2,5-bis (tertiary butylperoxide).
  • Oxy) hexyne-3 benzoyl peroxide, bis (2,4-dichlorobenzoyl) peroxide, dicumyl peroxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, tert-butyl peroxybenzene, 1,1 -Bis (tert-butylperoxy) -3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroxyperoxide, ⁇ , ⁇ '-bis (tert-butylperoxy) -p- Diisopropylbenzene, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tert-butylperoxyisopropyl carbonate and the like are used.
  • polyfunctional unsaturated compounds such as tri (meth) allyl isocyanurate, tri (meth) allyl cyanurate, triallyl trimellitate, N, N ⁇ -m-phenylene bismaleimide, diallyl phthalate, tris (diallylamine) -s-triazine, triallyl phosphite, 1,2-polybutadiene, ethylene glycol diacrylate, diethylene glycol diacrylate, etc. Used for the purpose of obtaining characteristics, mechanical strength, compression set characteristics and the like.
  • an oxide or hydroxide of a divalent metal for example, an oxide or hydroxide of calcium, magnesium, lead, zinc or the like can be used as a crosslinking aid. These compounds also act as acid acceptors.
  • Each of the above components to be blended in the peroxide crosslinking system generally contains about 0.1 to 10 parts by weight, preferably about 0.5 to 5 parts by weight of organic peroxide per 100 parts by weight of the fluorine-containing elastomer.
  • conventionally known fillers, reinforcing agents, plasticizers, lubricants, processing aids, pigments, and the like can be appropriately blended in the composition.
  • Peroxide crosslinking is performed by mixing the above components by a commonly used mixing method such as roll mixing, kneader mixing, Banbury mixing, solution mixing, and the like, followed by heating.
  • the heating is generally performed by press vulcanization performed at about 100 to 250 ° C. for about 1 to 120 minutes and oven vulcanization (secondary vulcanization) performed at about 150 to 300 ° C. for about 0 to 30 hours.
  • Reference example 1 In an autoclave with a capacity of 1200 ml equipped with a stirrer and a thermometer, CF 3 (CF 2 ) 3 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 I (99GC%) 603 g (0.99 mol) and 7 g (0.05 mol) of di-tert-butyl peroxide were charged, and the autoclave was deaerated with a vacuum pump. When the internal temperature was heated to 80 ° C., ethylene was sequentially introduced to adjust the internal pressure to 0.5 MPa. When the internal pressure decreased to 0.2 MPa, ethylene was introduced again to 0.5 MPa, and this was repeated.
  • Example 1 The 3,3,4,4,5,5,6,6,7,7,9 obtained in Reference Example 1 was added to a 50 ml glass reactor equipped with a cooling condenser, thermocouple and magnet stirrer. , 9,10,10,11,11,12,12,12-nonadecafluoro-1-iodododecane C 4 F 9 CH 2 (CF 2 ) 5 CH 2 CH 2 I 5 g (7.8 mmol) A solution dissolved in 15 ml of a solvent (Asahi Glass product AK-225) was charged and cooled with ice.
  • a solvent Asahi Glass product AK-225
  • Example 2 In Example 1, the amount of DBU used was changed to 1.3 g (8.5 mmol) for the reaction, and 1.2 g (yield 33%) of the product A-product B (weight ratio 48:52) mixture as the fraction. And 0.6 g (purity 98%, yield 15%) of the following product C, which is a fraction having a steam temperature of 76 to 77 ° C./1 kPa.
  • Example 3 In Example 1, 1.8 g (17.3 mmol) of triethylamine was used in place of DBU, and the reaction was carried out at a total reaction time of 48 hours. When the reaction was performed, the product A-product B (weight ratio 49:51) mixture as the fraction was obtained. 2.0 g (55% yield) and 1.0 g (26% yield) of the product C, the fraction, were obtained.
  • Example 4 In Example 3, the solvent was changed from a fluorine-containing organic solvent to 15 ml of tetrahydrofuran, the reaction temperature was changed to 50 ° C., the total reaction time was changed to 24 hours, and the product A-product B ( Weight ratio 49:51) 2.7 g (yield 74%) of the mixture was obtained.
  • Example 5 To a 50 ml glass reactor equipped with a cooling condenser, thermocouple and magnet stirrer, 3,3,4,4,5,5,7,7,8,8,9 obtained in Reference Example 2 above. , 9,10,10,10-Pentadecafluoro-1-iododecane C 4 F 9 CH 2 (CF 2 ) 3 CH 2 CH 2 I 5 g (9.3 mmol) in fluorinated organic solvent (Asahi Glass Products AK-225) 15 ml After being cooled in ice and cooled with ice, 3.0 g (19.7 mmol) of 1,8-diazabicyclo [5.4.0] -7-undecene [DBU] was maintained while maintaining the internal temperature in the range of 0 to 10 ° C. It was dripped. After completion of the dropwise addition, the mixture was stirred at about 0 ° C. for about 1 hour, and then stirred for about 23 hours at room temperature (total reaction time 24 hours).
  • TFE
  • a polymerization initiator aqueous solution in which 24 g of ammonium persulfate was dissolved in 500 g of water was pressed into the reactor to initiate the polymerization reaction.
  • the pressure in the reactor decreases, so the TFE / VdF / HFP (molar percentage 16.4 / 62.2 / 21.4) gas mixture is reacted so that the pressure is maintained at 3.75 to 3.85 MPa ⁇ G.
  • the total amount of the mixed gas was 10.2 kg
  • the addition was stopped (about 10 hours after the start of the reaction), and aging was performed for about 30 to 50 minutes.
  • the pressure in the reactor at that time was 1.8 MPa ⁇ G.
  • the reaction mixture was taken out of the reactor and coagulated with an aqueous calcium chloride solution to obtain fluorinated elastomer A.
  • the copolymer composition of the obtained fluorinated elastomer A was measured by NMR analysis, it was a VdF / TFE / HFP (molar percentage 67.1 / 16.0 / 16.9) copolymer.
  • an aqueous polymerization initiator solution in which 0.8 g of ammonium persulfate was dissolved in 500 g of water was injected into the reactor to initiate the polymerization reaction.
  • the pressure in the reactor decreases, so the TFE / VdF / FMVE (molar percentage 9.0 / 73.0 / 18.0) mixed gas is reacted so that the pressure is maintained at 3.0 to 2.9 MPa ⁇ G.
  • the total amount of the mixed gas reached 7.2 kg, the addition was stopped (about 4 hours after the start of the reaction), and aging was performed for about 120 minutes.
  • the pressure in the reactor at that time was 1.2 MPa ⁇ G.
  • the reaction mixture was taken out from the reactor and coagulated with an aqueous calcium chloride solution to obtain fluorinated elastomer B.
  • the copolymer composition of the obtained fluorinated elastomer B was measured by NMR analysis, it was a VdF / TFE / FMVE (molar percentage 72.8 / 9.0 / 18.2) copolymer.
  • Example 1 Comparative Example 1 In Example 1, the diene mixture was not used for the copolymerization reaction.
  • the copolymer composition of the obtained fluorinated elastomer C was a VdF / TFE / HFP (molar percentage 67.0 / 16.0 / 17.0) copolymer. Vulcanization using this fluorine-containing elastomer C was also carried out in the same manner as in Example 6.
  • the copolymer composition of the obtained fluorine-containing elastomer D was a VdF / TFE / FMVE (molar percentage 73.2 / 9.0 / 17.8) copolymer. Vulcanization using this fluorine-containing elastomer D was also carried out in the same manner as in Example 7.
  • Example 7 Comparative Example 3 In Example 7, the diene mixture was not used for the copolymerization reaction.
  • the copolymer composition of the obtained fluorinated elastomer E was a VdF / TFE / FMVE (molar percentage 73.0 / 9.0 / 18.0) copolymer. Vulcanization using this fluorine-containing elastomer E was also carried out in the same manner as in Example 7.

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Abstract

A polyfluoroalkadiene mixture represented by the general formula CF3(CF2)nCF=CH(CF2)m+1CH=CH2 [Ia] and the general formula CF3(CF2)n+1CH=CF(CF2)mCH=CH2 [Ib] (wherein n is an integer from 0 to 5 and m is an integer from 0 to 6) is obtained and manufactured as a mixed fraction of products [Ia] and [Ib] by causing an organic basic compound to react with a polyfluoroalkayl iodide represented by the general formula CF3(CF2)n+1CH2(CF2)m+1(CH2CH2)I [II]. This polyfluoroalkadiene mixture is a compound in which the number of CF2 groups linked to a perfluoroalkyl group is 5 or less, and is effectively used as a copolymeric monomer in the manufacture of resinoid- or elastomer-inclusive fluorine-based copolymers that are the active ingredient in finishing agents, such as a water repellants and mold release agents, etc.

Description

ポリフルオロアルカジエン混合物およびその製造法Polyfluoroalkadiene mixture and process for producing the same

　本発明は、ポリフルオロアルカジエン混合物およびその製造法に関する。さらに詳しくは、C6以下パーフルオロアルキル基を有する化合物であって、撥水撥油剤等の有効成分である含フッ素共重合体の製造時に共重合性単量体として用いられるポリフルオロアルカジエン混合物およびその製造法に関する。 The present invention relates to a polyfluoroalkadiene mixture and a process for producing the same. More specifically, a compound having a C 6 or less perfluoroalkyl group, polyfluoroalkadiene mixture used as a copolymerizable monomer in the production of the active ingredient is a fluorinated copolymer of the water and oil repellent, etc. And its manufacturing method.

　パーフルオロアルキルアルコールのアクリル酸誘導体、例えばCF3(CF2)7CH2CH2OCOCH=CH2は、繊維用撥水撥油剤合成モノマーとして多量に使用されている。また、そのアクリレートの原料となるパーフルオロアルキルアルコールは、界面活性剤等として広く使用されている(特許文献１参照)。 Acrylic acid derivatives of perfluoroalkyl alcohol, such as CF 3 (CF 2 ) 7 CH 2 CH 2 OCOCH═CH 2, are used in large quantities as a water / oil repellent synthetic monomer for fibers. In addition, perfluoroalkyl alcohol, which is a raw material for the acrylate, is widely used as a surfactant or the like (see Patent Document 1).

　このように、パーフルオロアルキル基を構造単位として有する化合物は、繊維、金属、ガラス、ゴム、樹脂等の表面にこれを適用することによって、表面改質性、撥水撥油性、防汚性、離型性、レベリング性などを向上させる効果のあることが一般に知られている。その中でも、パーフルオロアルキル基の炭素数がC8～C12である化合物(テロマー化合物)が上記の如き望ましい性能を最も発現し易いので、C8のテロマー化合物が特に好んで使用されている。 Thus, a compound having a perfluoroalkyl group as a structural unit can be applied to the surface of fibers, metals, glass, rubber, resins, etc., thereby improving surface modification, water / oil repellency, antifouling, It is generally known that there is an effect of improving releasability, leveling properties and the like. Among them, a C 8 telomer compound is particularly preferred because a compound (telomer compound) having a C 8 to C 12 perfluoroalkyl group is most likely to exhibit the desired performance as described above.

　一方で、特にC8～C12のパーフルオロアルキル基を有するテロマー化合物は、環境中で生物的に分解され、生体濃縮性、環境濃縮性の比較的高い化合物に変化することが報告されており、処理工程での暴露、廃棄物、処理基材等からの環境への放出、拡散などが懸念されている。また、パーフルオロアルキル基の炭素数が14以上の化合物では、それの物理化学的性状から取扱いが非常に困難であり、殆ど使用はされていないのが実情である。 On the other hand, telomer compounds having C 8 to C 12 perfluoroalkyl groups in particular have been reported to be biodegraded in the environment and converted to compounds with relatively high bioconcentration and environmental concentration. There are concerns about exposure in the treatment process, waste, release to the environment from the treated substrate, diffusion, and the like. In addition, in the case of a compound having 14 or more carbon atoms in the perfluoroalkyl group, it is very difficult to handle due to its physicochemical properties, and the fact is that it is hardly used.

　さらに、C8以上のパーフルオロアルキル基を有するテロマー化合物にあっては、それの製造プロセスにおいて、生体濃縮性の高いパーフルオロオクタン酸類の発生や混入が避けられない。 Furthermore, in a telomer compound having a C 8 or higher perfluoroalkyl group, generation or contamination of perfluorooctanoic acids with high bioconcentration properties cannot be avoided in the production process.

　そのため、このようなテロマー化合物を製造している各社は、それの製造からの撤退やC6以下のパーフルオロアルキル基を有する化合物への代替などを進めているが、パーフルオロアルキル基の炭素数が6以下の化合物では、処理基材表面での配向性が著しく低下し、また融点、ガラス転移点等がC8化合物と比べて著しく低いため、温度、湿度、応力、有機溶剤等の使用環境条件に大きな影響を受け、そこに求められる十分な性能が得られず、また耐久性などにも影響が出てくるようになる。 Therefore, companies that produce such telomer compounds, although promoted the use of alternative to compounds having a withdrawal or C 6 following a perfluoroalkyl group from its production, the carbon number of the perfluoroalkyl group in There 6 the following compounds were significantly reduced in orientation in the treated substrate surface and the melting point, glass transition point or the like is significantly lower than that C 8 compound, temperature, humidity, stress, the use of an organic solvent environment It is greatly influenced by the conditions, and sufficient performance required there is not obtained, and durability is also affected.

特公昭６３－２２２３７号公報Japanese Patent Publication No. 63-22237 特開平１０－１３０３４１号公報JP-A-10-130341 特開昭６３－３０８００８号公報Japanese Unexamined Patent Publication No. 63-308008 特公昭５８－４７２８号公報Japanese Patent Publication No.58-4728 特公昭５４－１５８５号公報Japanese Patent Publication No.54-1585

　本発明の目的は、パーフルオロアルキル基の連続したCF2基の数が5以下の化合物であって、撥水撥油剤、離型剤等の表面処理剤の有効成分となる樹脂状またはエラストマー状含フッ素共重合体の製造に際し、共重合性単量体として有効に用いられるポリフルオロアルカジエン混合物およびその製造法を提供することにある。 An object of the present invention is a compound in which the number of continuous CF 2 groups of perfluoroalkyl groups is 5 or less, and is a resinous or elastomeric material that is an active ingredient of a surface treatment agent such as a water / oil repellent and a release agent An object of the present invention is to provide a polyfluoroalkadiene mixture that is effectively used as a copolymerizable monomer in the production of a fluorinated copolymer and a method for producing the same.

　本発明によって、一般式
　　　CF3(CF2)nCF=CH(CF2)m+1CH=CH2　　　　　　　　　　　　〔Ia〕
および一般式
　　　CF3(CF2)n+1CH=CF(CF2)mCH=CH2　　　　　　　　　　　　〔Ib〕
(ここで、nは0～5の整数であり、mは0～6の整数である)で表わされるポリフルオロアルカジエン混合物が提供される。かかるポリフルオロアルカジエン混合物は、一般式
　　　CF3(CF2)n+1CH2(CF2)m+1(CH2CH2)I　　　　　　　　　　　 〔II〕
(ここで、nは0～5の整数であり、mは0～6の整数である)で表わされるポリフルオロアルキルアイオダイドに有機塩基性化合物を反応させ、生成物〔Ia〕および〔Ib〕の混合物留分として取得することによって製造される。 According to the present invention, the general formula CF 3 (CF 2 ) n CF═CH (CF 2 ) m + 1 CH═CH 2 [Ia]
And the general formula CF 3 (CF 2 ) n + 1 CH = CF (CF 2 ) m CH = CH 2 (Ib)
(Where n is an integer from 0 to 5 and m is an integer from 0 to 6). Such polyfluoroalkadiene mixtures have the general formula CF 3 (CF 2 ) n + 1 CH 2 (CF 2 ) m + 1 (CH 2 CH 2 ) I [II]
(Where n is an integer of 0 to 5 and m is an integer of 0 to 6) is reacted with an organic basic compound, and the products [Ia] and [Ib] It is manufactured by obtaining as a mixture fraction.

　本発明に係るポリフルオロアルカジエン混合物は、環境中へ放出されたときそれが容易にオゾン分解などされて、環境濃縮性、生体蓄積性の低い化合物へと分解され易い不飽和構造を有し、またその製造工程でパーフルオロアルキルカルボン酸等の環境負荷物質を生成させない。 The polyfluoroalkadiene mixture according to the present invention has an unsaturated structure that is easily decomposed into ozonolysis when released into the environment, and is easily decomposed into a compound having low environmental accumulation and bioaccumulation, In addition, environmentally hazardous substances such as perfluoroalkyl carboxylic acids are not generated in the manufacturing process.

　このような環境面ですぐれている本発明のポリフルオロアルカジエン混合物は、C8テロマーと比較してC6以下のテロマーでは発現できないあるいは不足している表面改質性、撥水撥油性、防汚性、離型性、レベリング性などの性能面をも改善できる含フッ素共重合体製造用の共重合性単量体として、有効に使用することができる。 Such polyfluoroalkadiene mixture of good and that the present invention environmental surfaces, C 8 telomer compared to the surface modification of the C 6 following telomers missing or can not be expressed, water- and oil-repellency, anti It can be effectively used as a copolymerizable monomer for producing a fluorinated copolymer that can improve performance such as soiling, releasability and leveling.

　また、ポリフルオロアルカジエン混合物をフッ素化オレフィン単量体に共重合させて得られた含フッ素共重合体は、含フッ素エラストマーとしてパーオキサイド架橋が可能である。 Further, the fluorine-containing copolymer obtained by copolymerizing a polyfluoroalkadiene mixture with a fluorinated olefin monomer can be peroxide-crosslinked as a fluorine-containing elastomer.

　本発明にかかるポリフルオロアルカジエン混合物は、一般式
　　　CF3(CF2)nCH2(CF2)m+1(CH2CH2)I　　　　　　　　　　　 〔II〕
　　　　　　　n：0～5
　　　　　　　m：0～6
で表わされるポリフルオロアルキルアイオダイドに有機塩基性化合物を反応させ、脱HI化反応させると共に、-CF2CH2CF2-結合を脱HF化反応させることにより、生成物〔Ia〕と〔Ib〕との混合物として製造される。 The polyfluoroalkadiene mixture according to the present invention has the general formula CF 3 (CF 2 ) n CH 2 (CF 2 ) m + 1 (CH 2 CH 2 ) I [II]
n: 0 to 5
m: 0-6
The product [Ia] and [Ib] are produced by reacting an organic basic compound with the polyfluoroalkyl iodide represented by the formula ( II) and dehydrating it, and deHFing the —CF 2 CH 2 CF 2 — bond. ] As a mixture.

　ここで化合物〔Ia〕および〔Ib〕の混合物として形成されるのは、脱HI化反応と共に行われる脱HF化反応において、メチレン鎖CH2のH原子とこれと前後の位置に結合しているフルオロメチレン鎖CF2のいずれか一方のF原子との引き抜きが、前後で等価的に生ずるためである。また、生成したポリフルオロアルカジエン混合物は、脱HF化反応が等価的であるため、生成物〔Ia〕と〔Ib〕の生成割合はほぼ半々となる。これらの生成物〔Ia〕と〔Ib〕とは、極めて類似した構造異性体であるため、それぞれを分離して同定することはできないが、同等の反応性を有するため、混合物のままそれを他の物質の合成原料として用いることができる。 Here, the compound [Ia] and [Ib] formed as a mixture are bonded to the H atom of the methylene chain CH 2 and the front and back positions in the deHF reaction carried out together with the deHI reaction. This is because extraction with any one F atom of the fluoromethylene chain CF 2 occurs equivalently before and after. Further, since the resulting polyfluoroalkadiene mixture is equivalent to the deHF reaction, the production ratio of the products [Ia] and [Ib] is almost halved. Since these products [Ia] and [Ib] are very similar structural isomers, they cannot be separated and identified, but they have the same reactivity, so that they remain as a mixture. It can be used as a raw material for the synthesis of

　出発原料物質となるポリフルオロアルキルアイオダイドは、例えばn=3、m+1=5または3の化合物の場合、後記参考例に示される如き方法で得られる。 The polyfluoroalkyl iodide used as a starting material is obtained by a method as shown in Reference Examples described later in the case of a compound of n = 3, m + 1 = 5 or 3, for example.

　また、ポリフルオロアルキルアイオダイドは、末端ヨウ素化ポリフルオロアルカンにエチレンを付加反応させることにより得られる。末端ヨウ素化ポリフルオロアルカンとしては、例えば次のような化合物が挙げられる。
　　　CF3(CF2)(CH2CF2)I
　　　CF3(CF2)2(CH2CF2)I
　　　CF3(CF2)3(CH2CF2)I
　　　CF3(CF2)4(CH2CF2)I
　　　CF3(CF2)(CH2CF2)(CF2CF2)I
　　　CF3(CF2)(CH2CF2)(CF2CF2)2I
　　　CF3(CF2)2(CH2CF2)(CF2CF2)I
　　　CF3(CF2)2(CH2CF2)(CF2CF2)2I Polyfluoroalkyl iodide can be obtained by addition reaction of terminally iodized polyfluoroalkane with ethylene. Examples of the terminal iodinated polyfluoroalkane include the following compounds.
CF 3 (CF 2 ) (CH 2 CF 2 ) I
CF 3 (CF 2 ) 2 (CH 2 CF 2 ) I
CF 3 (CF 2 ) 3 (CH 2 CF 2 ) I
CF 3 (CF 2 ) 4 (CH 2 CF 2 ) I
CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) I
CF 3 (CF 2 ) (CH 2 CF 2 ) (CF 2 CF 2 ) 2 I
CF 3 (CF 2 ) 2 (CH 2 CF 2 ) (CF 2 CF 2 ) I
CF 3 (CF 2 ) 2 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 I

　ポリフルオロアルキルアイオダイド
　　　CF3(CF2)n+1CH2(CF2)m+1(CH2CH2)I　　　　　　　　　　　 〔II〕
すなわち
　　　CH3(CF2)n+1(CH2CF2)(CF2CF2)p(CH2CH2)I　　　(ただし、m=2p)
は、一般式
　　　CF3(CF2)n+1(CH2CF2)(CF2CF2)pI　　　　　　　　　　　　 〔A〕
で表わされる末端ヨウ素化化合物にエチレンを付加反応させることにより製造される。 Polyfluoroalkyl iodide CF 3 (CF 2 ) n + 1 CH 2 (CF 2 ) m + 1 (CH 2 CH 2 ) I (II)
That is, CH 3 (CF 2 ) n + 1 (CH 2 CF 2 ) (CF 2 CF 2 ) p (CH 2 CH 2 ) I (where m = 2p)
Is the general formula CF 3 (CF 2 ) n + 1 (CH 2 CF 2 ) (CF 2 CF 2 ) p I (A)
It is produced by addition reaction of ethylene with a terminal iodinated compound represented by the formula:

　エチレンの付加反応は、上記化合物〔A〕に過酸化物開始剤の存在下で加圧エチレンを付加反応させることにより行われ、その付加数は反応条件にもよるが、1以上、好ましくは1である。なお、反応温度は用いられる開始剤の分解温度にも関係するが、反応は一般に約80～120℃で行われ、低温で分解する過酸化物開始剤を用いた場合には80℃以下での反応が可能である。過酸化物開始剤としては、第3ブチルパーオキサイド、ジ(第3ブチルシクロヘキシル)パーオキシジカーボネート、ジセチルパーオキシジカーボネート等が、上記化合物〔A〕に対して約1～5モル％の割合で用いられる。 The addition reaction of ethylene is carried out by subjecting the above compound [A] to addition reaction of pressurized ethylene in the presence of a peroxide initiator. The number of additions depends on the reaction conditions, but it is 1 or more, preferably 1 It is. Although the reaction temperature is related to the decomposition temperature of the initiator used, the reaction is generally carried out at about 80 to 120 ° C. When a peroxide initiator that decomposes at a low temperature is used, the reaction temperature is 80 ° C. or less. Reaction is possible. As the peroxide initiator, tertiary butyl peroxide, di (tertiary butyl cyclohexyl) peroxydicarbonate, dicetyl peroxydicarbonate and the like are used in an amount of about 1 to 5 mol% with respect to the compound [A]. Used in proportions.

　ポリフルオロアルカンアイオダイド〔II〕に有機塩基性化合物を反応させ、脱ハロゲン化水素化反応させることにより、1-位の脱HI化反応およびパーフルオロアルキル基側のCH2基とそれに隣接する２つのCF2基のいずれかとの間の脱HF化反応が生じ、ポリフルオロアルカジエン〔Ia〕および〔Ib〕の混合物を生成させる。 By reacting a polyfluoroalkane iodide [II] with an organic basic compound and dehydrohalogenating it, the 1-position de-HI reaction and the perfluoroalkyl group side CH 2 group and the adjacent 2 A deHF reaction occurs between any of the two CF 2 groups to produce a mixture of polyfluoroalkadiene [Ia] and [Ib].

　有機塩基性化合物としては、例えばジエチルアミン、トリエチルアミン、ピリジンまたはその誘導体、ジエタノールアミン、トリエタノールアミン、1,8-ジアザビシクロ〔5.4.0〕-7-ウンデセン、ジアザビシクロノネン等の含窒素有機塩基性化合物、ナトリウムメトキシド、ナトリウムエトキシド、カリウムメトキシド等の1価金属アルコキシドが挙げられ、好ましくは求核性の低い含窒素有機塩基性化合物、特に好ましくは1,8-ジアザビシクロ〔5.4.0〕-7-ウンデセンが用いられる。 Examples of organic basic compounds include nitrogen-containing organic basic compounds such as diethylamine, triethylamine, pyridine or derivatives thereof, diethanolamine, triethanolamine, 1,8-diazabicyclo [5.4.0] -7-undecene, diazabicyclononene, etc. Monovalent metal alkoxides such as sodium methoxide, sodium ethoxide and potassium methoxide, preferably nitrogen-containing organic basic compounds with low nucleophilicity, particularly preferably 1,8-diazabicyclo [5.4.0]- 7-Undecene is used.

　これらの有機塩基性化合物は、ポリフルオロアルカンアイオダイド〔II〕に対してモル比で約0.1～10、好ましくは0.95～3.5、さらに好ましくは1.95～2.5の割合で用いられる。さらに好ましいモル比である1.95～2.5の割合で、1,8-ジアザビシクロ〔5.4.0〕-7-ウンデセンが含フッ素有機溶媒中で用いられた場合あるいはトリエチルアミンがテトラヒドロフラン溶媒中で用いられた場合には、専らポリフルオロアルカジエン混合物〔Ia〕、〔Ib〕が、75％前後の収率で生成する。他の場合には生成物〔Ia〕、〔Ib〕と共に、C4F9CH2(CF2)4CH=CH2等が副生するが、これらの副生成物とは分留による分離が可能である。有機塩基性化合物の使用割合がこれよりも少ないと、所望の脱ハロゲン化水素反応が円滑に進行せず、一方これよりも多い使用割合で用いられると、有機塩基性化合物の除去が困難となるばかりではなく、副反応を誘発するなどの問題が生じ、廃棄物量が増加することになる。 These organic basic compounds are used in a molar ratio of about 0.1 to 10, preferably 0.95 to 3.5, more preferably 1.95 to 2.5 with respect to polyfluoroalkane iodide [II]. When 1,8-diazabicyclo [5.4.0] -7-undecene is used in a fluorine-containing organic solvent at a preferred molar ratio of 1.95 to 2.5, or when triethylamine is used in a tetrahydrofuran solvent. Produces exclusively a polyfluoroalkadiene mixture [Ia], [Ib] with a yield of around 75%. In other cases, C 4 F 9 CH 2 (CF 2 ) 4 CH═CH 2 etc. are by-produced together with the products [Ia] and [Ib], but these by-products are separated by fractional distillation. Is possible. When the proportion of the organic basic compound used is less than this, the desired dehydrohalogenation reaction does not proceed smoothly. On the other hand, when the proportion used is higher than this, it is difficult to remove the organic basic compound. In addition to problems such as inducing side reactions, the amount of waste increases.

　脱ハロゲン化水素化反応は、無溶媒でも行われるが、反応効率、発熱制御の観点から、水または有機溶媒の存在下で行うことが好ましい。有機溶媒としては、メタノール、エタノール、プロパノール、イソプロパノール等のアルコール類、ジエチルエーテル、1,4-ジオキサン、テトラヒドロフラン等のエーテル類、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類、トルエン、シクロヘキサン等の芳香族または脂環式炭化水素類、アセトニトリル、N,N-ジメチルホルムアミド、N,N-ジエチルホルムアミド、N,N-ジメチルアセトアミド、N,N-ジエチルアセトアミド、N-メチル-2-ピロリドン等の非プロトン性極性溶媒、HCFC-225等のハイドロクロロフルオロカーボン、ハイドロフルオロエーテル(例えば、3M社製品ノベックHFE)等の含フッ素有機溶媒が用いられる。 The dehydrohalogenation reaction is carried out without a solvent, but is preferably carried out in the presence of water or an organic solvent from the viewpoint of reaction efficiency and heat generation control. Examples of the organic solvent include alcohols such as methanol, ethanol, propanol and isopropanol, ethers such as diethyl ether, 1,4-dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and aromatics such as toluene and cyclohexane. Aprotic such as aromatic or alicyclic hydrocarbons, acetonitrile, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone Polar solvents, hydrochlorofluorocarbons such as HCFC-225, and fluorine-containing organic solvents such as hydrofluoroethers (for example, 3M product Novec HFE) are used.

　水または有機溶媒は、ポリフルオロアルカンアイオダイド〔II〕に対して容積比で約0.1～100、好ましくは約1～10、さらに好ましくは3～6の割合で用いられる。ただし、溶媒量を多くしても反応効率に影響がみられないため、3～6の容量比で用いることが好ましい。 Water or an organic solvent is used in a volume ratio of about 0.1 to 100, preferably about 1 to 10, and more preferably 3 to 6 with respect to the polyfluoroalkane iodide [II]. However, since the reaction efficiency is not affected even if the amount of the solvent is increased, it is preferably used in a volume ratio of 3 to 6.

　脱ハロゲン化水素化反応は、約-20～100℃、好ましくは約-10～80℃で行われる。これよりも高い温度では、副反応が進行し、構造不明な副生成物が多量に発生する。反応圧力については、減圧下、大気圧下、加圧下のいずれでもよく、反応装置の簡便性からは大気圧下で行うことが好ましい。 The dehydrohalogenation reaction is performed at about -20 to 100 ° C, preferably about -10 to 80 ° C. At temperatures higher than this, side reactions proceed and a large amount of by-products with unknown structures are generated. The reaction pressure may be any of reduced pressure, atmospheric pressure, and pressurized pressure, and it is preferable to carry out the reaction at atmospheric pressure for the convenience of the reaction apparatus.

　反応終了後静置分相する場合には、分液された有機層を水洗などにより有機塩基性化合物を除去した後、定法にしたがって蒸留などによる精製を行い、目的物であるポリフルオロアルカジエン混合物を得ることができる。極性溶媒を用いるなどして静置分相しない場合には、溶媒を減圧下で留去した後、静置分相する場合と同様な処理が行われる。 In the case of phase separation after completion of the reaction, after removing the organic basic compound by washing the separated organic layer with water, etc., purifying by distillation etc. according to a conventional method, the target polyfluoroalkadiene mixture Can be obtained. When the stationary phase separation is not performed by using a polar solvent, for example, the solvent is distilled off under reduced pressure and then the same treatment as in the case of stationary phase separation is performed.

　このようにして得られるポリフルオロアルカジエン混合物は、例えば一般式
　　　CX2=CXY
で表わされるフッ素化オレフィン単量体と共重合させて含フッ素エラストマーを形成させる。ここで、
　　　X：H、F
　　　Y：H、F、CnF2n+1(n：1～3)、O〔CF(Z)CF2O〕mCnF2n+1(Z：F、CF3、n：1～3
　　　　 、m：0～5)
であり、X、Yは同一または異なり、その少なくとも一つはF原子または含フッ素基である。 The polyfluoroalkadiene mixture obtained in this way has, for example, the general formula CX 2 = CXY
To form a fluorine-containing elastomer. here,
X: H, F
Y: H, F, C n F 2n + 1 (n: 1 to 3), O [CF (Z) CF 2 O] m C n F 2n + 1 (Z: F, CF 3 , n: 1 to 3
, M: 0-5)
X and Y are the same or different, and at least one of them is an F atom or a fluorine-containing group.

　ポリフルオロアルカジエン混合物が共重合される、上記一般式で示されるフッ素化オレフィン単量体としては、例えばフッ化ビニリデン、テトラフルオロエチレン、ヘキサフルオロプロピレン、低級アルキルが炭素数1～3のパーフルオロ(低級アルキルビニルエーテル)、一般式CF2=CFO〔CF(CF3)CF2O〕nCF3(n：1～5)で表わされるパーフルオロビニルエーテル等の少くとも一種が用いられ、具体的にはフッ化ビニリデン-テトラフルオロエチレン共重合体、フッ化ビニリデン-テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体、フッ化ビニリデン-テトラフルオロエチレン-パーフルオロ(低級アルキルビニルエーテル)等のフッ化ビニリデン-テトラフルオロエチレン系共重合体が好ましい含フッ素エラストマーとして挙げられる。 Examples of the fluorinated olefin monomer represented by the above general formula in which the polyfluoroalkadiene mixture is copolymerized include vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, and lower alkyl perfluorocarbons having 1 to 3 carbon atoms. (Lower alkyl vinyl ether), at least one kind of perfluorovinyl ether represented by the general formula CF 2 = CFO [CF (CF 3 ) CF 2 O] n CF 3 (n: 1 to 5) is used. Is vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene-perfluoro (lower alkyl vinyl ether), etc. Ethylene copolymers are mentioned as preferred fluorine-containing elastomers.

　これらの含フッ素エラストマー中に約1.5モル％以下、好ましくは約0.02～0.5モル％の割合(仕込み全単量体に対して約5重量％以下、好ましくは約0.1～2重量％の割合)で共重合されるポリフルオロアルカジエン混合物は、それぞれが反応性の異なる2種類の不飽和結合を有する2官能性単量体であり、ポリフルオロアルカジエンを共重合させない含フッ素エラストマーあるいはポリフルオロアルカジエンの代りに一般式CF2=CF〔OCF2CF(CF3)〕mOCF2CF2O〔CF(CF3)CF2O〕nCF=CF2(ただし、m+nは0～8の整数である)で表わされる他の2官能性単量体を共重合させた含フッ素エラストマーと比較して、加硫物性および耐圧縮永久歪特性にすぐれた含フッ素エラストマー架橋物を与えることができる。 In these fluorine-containing elastomers, the proportion is about 1.5 mol% or less, preferably about 0.02 to 0.5 mol% (about 5 wt% or less, preferably about 0.1 to 2 wt% based on the total amount of charged monomers). The polyfluoroalkadiene mixture to be copolymerized is a bifunctional monomer having two types of unsaturated bonds, each having different reactivity, and is a fluorine-containing elastomer or polyfluoroalkadiene that does not copolymerize polyfluoroalkadiene. Instead of the general formula CF 2 = CF [OCF 2 CF (CF 3 )] m OCF 2 CF 2 O [CF (CF 3 ) CF 2 O] n CF = CF 2 (where m + n is 0-8) Compared with a fluorine-containing elastomer copolymerized with another bifunctional monomer represented by (an integer), a crosslinked fluorine-containing elastomer having excellent vulcanization properties and compression set resistance can be provided. .

　含フッ素エラストマー中に多官能性不飽和単量体を共重合させると、架橋物の耐圧縮永久歪特性が改善されることは従来から知られているが、この特性が改善される反面で、架橋物の加硫物性、特に破断時伸び特性の低下が避けられないという問題がみられる。この問題は、多官能性不飽和単量体の不飽和官能性基間の構造の変更(鎖長の調整)により改善させる可能性が考えられるが、耐圧縮永久歪特性と加硫物性、特に伸び特性とは、トレードオフの関係にあり、これら両者の特性を同時に満足させることはできないが、本発明に係るポリフルオロアルカジエンの共重合は、得られる含フッ素エラストマーのこれら両者の特性の両立を可能としている。 It has been conventionally known that when a polyfunctional unsaturated monomer is copolymerized in a fluorine-containing elastomer, the compression set resistance of the cross-linked product is improved. However, while this characteristic is improved, There is a problem that the vulcanized physical properties of the cross-linked product, particularly the elongation at break, cannot be avoided. This problem may be improved by changing the structure between the unsaturated functional groups of the polyfunctional unsaturated monomer (adjusting the chain length), but the compression set resistance and vulcanization properties, especially The elongation characteristics are in a trade-off relationship, and it is impossible to satisfy both of these characteristics at the same time. However, the copolymerization of the polyfluoroalkadiene according to the present invention achieves both of the characteristics of the obtained fluorine-containing elastomer. Is possible.

　かかるポリフルオロアルカジエン混合物と共に、臭素基含有またはヨウ素基含有不飽和単量体化合物、好ましくは臭素基含有不飽和単量体化合物を、フルオロエラストマー中約5モル％以下、好ましくは約1モル％共重合させることができ、それによって得られるフルオロエラストマーの架橋特性、具体的には破断時伸び、破断強度、耐圧縮永久歪特性などをさらに改善させることができる。 A bromine group-containing or iodine group-containing unsaturated monomer compound, preferably a bromine group-containing unsaturated monomer compound, together with such a polyfluoroalkadiene mixture is contained in the fluoroelastomer in an amount of about 5 mol% or less, preferably about 1 mol%. The crosslinking properties of the fluoroelastomer obtained by the copolymerization, specifically, elongation at break, strength at break, resistance to compression set, and the like can be further improved.

　臭素基含有不飽和単量体化合物としては、例えば臭化ビニル、2-ブロモ-1,1-ジフルオロエチレン、パーフルオロアリルブロマイド、4-ブロモ-1,1,2-トリフルオロブテン-1、4-ブロモ-3,3,4,4-テトラフルオロブテン-1、4-ブロモ-1,1,3,3,4,4-ヘキサフルオロブテン-1、ブロモトリフルオロエチレン、4-ブロモ-3-クロロ-1,1,3,4,4-ペンタフルオロブテン-1、6-ブロモ-5,5,6,6-テトラフルオロヘキセン-1、4-ブロモパーフルオロブテン-1、3,3-ジフルオロアリルブロマイド等の臭素化ビニル化合物または臭素化オレフィンを用いることができるが、好ましくは次の一般式で表わされるような臭素基含有ビニルエーテルが用いられる。
　　　　BrRf-O-CF=CF2
　　　　　　　　BrRf：臭素基含有パーフルオロアルキル基
かかる臭素基含有ビニルエーテルとしては、例えば BrCF2CF2OCF=CF2、BrCF2(CF2)2OCF=CF2、BrCF2(CF2)3OCF=CF2、CF3CFBr(CF2)2OCF=CF2、BrCF2(CF2)4OCF=CF2等が用いられる。 Examples of bromine group-containing unsaturated monomer compounds include vinyl bromide, 2-bromo-1,1-difluoroethylene, perfluoroallyl bromide, 4-bromo-1,1,2-trifluorobutene-1, 4 -Bromo-3,3,4,4-tetrafluorobutene-1, 4-bromo-1,1,3,3,4,4-hexafluorobutene-1, bromotrifluoroethylene, 4-bromo-3- Chloro-1,1,3,4,4-pentafluorobutene-1, 6-bromo-5,5,6,6-tetrafluorohexene-1, 4-bromoperfluorobutene-1, 3,3-difluoro A brominated vinyl compound such as allyl bromide or a brominated olefin can be used, but a bromine group-containing vinyl ether represented by the following general formula is preferably used.
BrRf-O-CF = CF 2
BrRf: bromine group-containing perfluoroalkyl group Examples of such bromine group-containing vinyl ethers include BrCF 2 CF 2 OCF = CF 2 , BrCF 2 (CF 2 ) 2 OCF = CF 2 , BrCF 2 (CF 2 ) 3 OCF = CF 2 CF 3 CFBr (CF 2 ) 2 OCF = CF 2 , BrCF 2 (CF 2 ) 4 OCF = CF 2 and the like are used.

　また、ヨウ素含有不飽和単量体化合物としては、ヨードトリフルオロエチレン、1,1-ジフルオロ-2-ヨードエチレン、パーフルオロ(2-ヨードエチルビニルエーテル)、ヨウ化ビニル等が用いられる。 As the iodine-containing unsaturated monomer compound, iodotrifluoroethylene, 1,1-difluoro-2-iodoethylene, perfluoro (2-iodoethyl vinyl ether), vinyl iodide, or the like is used.

　これらの臭素基含有またはヨウ素基含有不飽和単量体化合物に代えて、あるいはそれと共に、一般式R(Br)n(I)m (ここで、Rは炭素数2～6の飽和フルオロ炭化水素基または飽和クロロフルオロ炭化水素基であり、n、mは0.1または2であり、かつm+nは2である)で表わされる含臭素および／またはヨウ素化合物を用い、これらの化合物の存在下でポリフルオロアルカジエンと他のフッ素化オレフィン単量体との共重合反応を行うことができる。これらの含臭素および／またはヨウ素化合物は周知の化合物であり、例えば特許文献２～５に記載されている。 Instead of or together with these bromine group-containing or iodine group-containing unsaturated monomer compounds, R (Br) n (I) m (wherein R is a saturated fluorohydrocarbon having 2 to 6 carbon atoms) Or a saturated chlorofluorohydrocarbon group, n, m is 0.1 or 2, and m + n is 2) in the presence of these compounds. A copolymerization reaction of polyfluoroalkadiene and other fluorinated olefin monomers can be carried out. These bromine-containing and / or iodine compounds are well-known compounds and are described, for example, in Patent Documents 2 to 5.

　また、かかる化合物を用いることにより、これらの化合物が連鎖移動剤として作用し、生成する含フッ素共重合体の分子量を調節する働きをなし、また連鎖移動反応の結果として分子末端に臭素および／またはヨウ素原子が結合した含フッ素共重合体が得られ、これらの部位は硬化部位を形成される。すなわち、連鎖移動剤として、公知の一般式ICnF2nIで表わされるヨウ化物、例えばI(CF2)4Iや一般式ICnF2nBrで表わされるハロゲン化物、例えばIC(CF2)4Br、I(CF2)2Brを併せ用いた場合には、ハロゲン原子が分子末端に結合してなおラジカル的に活性な状態であるため、パーオキサイド架橋可能な架橋点として利用できる利点もみられる。 In addition, by using such compounds, these compounds act as chain transfer agents and serve to regulate the molecular weight of the resulting fluorinated copolymer, and as a result of the chain transfer reaction, bromine and / or A fluorine-containing copolymer having iodine atoms bonded thereto is obtained, and these sites form cured sites. That is, as a chain transfer agent, a known iodide represented by the general formula IC n F 2n I, such as a halide represented by I (CF 2 ) 4 I or a general formula IC n F 2n Br, such as IC (CF 2 ), for example. When 4 Br and I (CF 2 ) 2 Br are used in combination, the halogen atom is bonded to the molecular end and is still radically active. It is done.

　共重合反応は、水性乳化重合法または水性けん濁重合法によって行われる。水性乳化重合法では、水溶性過酸化物を単独であるいはそれと水溶性還元性物質とを組み合せたレドックス系のいずれをも、反応開始剤系として用いることができる。水溶性過酸化物としては、例えば過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウム等が、また水溶性還元性物質としては、例えば亜硫酸ナトリウム、亜硫酸水素ナトリウム等が用いられる。この際、生成した水性乳化液の安定化剤として、pH調節剤(緩衝剤)、例えばリン酸一水素ナトリウム、リン酸二水素ナトリウム、リン酸一水素カリウム、リン酸二水素カリウム等も用いられる。 The copolymerization reaction is performed by an aqueous emulsion polymerization method or an aqueous suspension polymerization method. In the aqueous emulsion polymerization method, either a water-soluble peroxide alone or a redox system in combination with a water-soluble reducing substance can be used as a reaction initiator system. Examples of water-soluble peroxides include ammonium persulfate, potassium persulfate, and sodium persulfate. Examples of water-soluble reducing substances include sodium sulfite and sodium bisulfite. At this time, a pH regulator (buffering agent) such as sodium monohydrogen phosphate, sodium dihydrogen phosphate, potassium monohydrogen phosphate, potassium dihydrogen phosphate, etc. is also used as a stabilizer for the produced aqueous emulsion. .

　乳化重合反応は、一般式　RfCOOM
　　　　　　　　　　Rf：フルオロアルキル基
　　　　　　　　　　　　パーフルオロアルキル基
　　　　　　　　　　　　フルオロオキシアルキル基
　　　　　　　　　　　　パーフルオロオキシアルキル基など
　　　　　　　　　　 M：アンモニウム塩、アルカリ金属
で表わされる乳化剤の存在下で行われる。乳化剤の使用量は、水に対して約0.1～20重量％、好ましくは約0.2～2重量％である。 The emulsion polymerization reaction has the general formula RfCOOM
Rf: Fluoroalkyl group Perfluoroalkyl group Fluorooxyalkyl group Perfluorooxyalkyl group, etc. M: Performed in the presence of an ammonium salt or an emulsifier represented by an alkali metal. The amount of the emulsifier used is about 0.1 to 20% by weight, preferably about 0.2 to 2% by weight, based on water.

　上記一般式で表わされる乳化剤としては、次のようなものが例示される。
　　C5F11COONH4　　　　　　　　　　  　　 　C5F11COONa
　　C6F13COONH4　　　　　　　　　　  　　 　C6F13COONH4Na
　　C6HF12COONH4　　　　　　　　　  　　  　C6HF12COONH4Na
　　C6H2F11COONH4　　　　　　　　　 　　  　C6H2F11COONH4Na
　　C7F15COONH4　　　　　　　　　　  　　 　C7F15COONH4Na
　　C7HF14COONH4　　　　　　　　　　  　　　C7HF14COONH4Na
　　C7H2F13COONH4　　　　　　　　　　 　  　C7H2F13COONH4Na
　　C8F17COONH4　　　　　　　　　　　  　 　C8F17COONH4Na
　　C8HF16COONH4　　　　　　　　　　　　　　C8HF16COONH4Na
　　C8H2F15COONH4　　　　　　　　　　　   　C8H2F15COONH4Na
　　C9F19COONH4　　　　　　　　　　　　   　C9F19COONH4Na
　　C9HF18COONH4　　　　　　　　　　　　  　C9HF18COONH4Na
　　C9H2F17COONH4　　　　　　　　　　　　 　C9H2F17COONH4Na
　　C3F7OCF(CF3)COONH4　　　　　　　　　  　C3F7OCF(CF3)COONH4Na
　　C3F7OCF(CF3)CF2OCF(CF3)COONH4　　　　 
　　C3F7OCF(CF3)CF2OCF(CF3)COONH4Na
　　C3F7O〔CF(CF3)CF2O〕2CF(CF3)COONH4　
　　C3F7O〔CF(CF3)CF2O〕2CF(CF3)COONH4Na
　　C3F7O〔CF(CF3)CF2O〕3CF(CF3)COONH4　
　　C3F7O〔CF(CF3)CF2O〕3CF(CF3)COONH4Na The following are illustrated as an emulsifier represented by the said general formula.
C 5 F 11 COONH 4 C 5 F 11 COONa
C 6 F 13 COONH 4 C 6 F 13 COONH 4 Na
C 6 HF 12 COONH 4 C 6 HF 12 COONH 4 Na
C 6 H 2 F 11 COONH 4 C 6 H 2 F 11 COONH 4 Na
C 7 F 15 COONH 4 C 7 F 15 COONH 4 Na
C 7 HF 14 COONH 4 C 7 HF 14 COONH 4 Na
C 7 H 2 F 13 COONH 4 C 7 H 2 F 13 COONH 4 Na
C 8 F 17 COONH 4 C 8 F 17 COONH 4 Na
C 8 HF 16 COONH 4 C 8 HF 16 COONH 4 Na
C 8 H 2 F 15 COONH 4 C 8 H 2 F 15 COONH 4 Na
C 9 F 19 COONH 4 C 9 F 19 COONH 4 Na
C 9 HF 18 COONH 4 C 9 HF 18 COONH 4 Na
C 9 H 2 F 17 COONH 4 C 9 H 2 F 17 COONH 4 Na
C 3 F 7 OCF (CF 3 ) COONH 4 C 3 F 7 OCF (CF 3 ) COONH 4 Na
C 3 F 7 OCF (CF 3 ) CF 2 OCF (CF 3 ) COONH 4
C 3 F 7 OCF (CF 3 ) CF 2 OCF (CF 3 ) COONH 4 Na
C 3 F 7 O (CF (CF 3 ) CF 2 O) 2 CF (CF 3 ) COONH 4
C 3 F 7 O [CF (CF 3 ) CF 2 O] 2 CF (CF 3 ) COONH 4 Na
C 3 F 7 O (CF (CF 3 ) CF 2 O) 3 CF (CF 3 ) COONH 4
C 3 F 7 O [CF (CF 3 ) CF 2 O] 3 CF (CF 3 ) COONH 4 Na

　分子量の調節は、共重合速度と開始剤量との関係を調整して行うことも可能であるが、連鎖移動剤、例えばC4～C6炭化水素類、アルコール類、エーテル類、エステル類、ケトン類、有機ハロゲン化物等を使用することによっても、容易に行うことができる。 The molecular weight can be adjusted by adjusting the relationship between the copolymerization rate and the initiator amount. However, chain transfer agents such as C 4 to C 6 hydrocarbons, alcohols, ethers, esters, It can also be easily carried out by using ketones, organic halides and the like.

　反応温度および反応圧力については、用いられる開始剤の分解温度や求められる共重合体の共重合組成によっても異なるが、エラストマー状共重合体を得るためには、約0～100℃、好ましくは約40～80℃、約0.8～4.5MPa・G、好ましくは約0.8～4.2MPa・Gという反応条件が一般に用いられる。 The reaction temperature and reaction pressure vary depending on the decomposition temperature of the initiator used and the copolymer composition required, but in order to obtain an elastomeric copolymer, about 0 to 100 ° C., preferably about Reaction conditions of 40-80 ° C., about 0.8-4.5 MPa · G, preferably about 0.8-4.2 MPa · G are generally used.

　このようにして得られる含フッ素エラストマーは、共重合体中にパーオキサイド架橋性基として作用するフルオロオレフィンアイオダイド混合物由来のヨウ素等を有しているので、有機過酸化物によってパーオキサイド架橋される。パーオキサイド架橋に用いられる有機過酸化物としては、例えば2,5-ジメチル-2,5-ビス(第3ブチルパーオキシ)ヘキサン、2,5-ジメチル-2,5-ビス(第3ブチルパーオキシ)ヘキシン-3、ベンゾイルパーオキシド、ビス(2,4-ジクロロベンゾイル)パーオキシド、ジクミルパーオキシド、ジ第3ブチルパーオキシド、第3ブチルクミルパーオキシド、第3ブチルパーオキシベンゼン、1,1-ビス(第3ブチルパーオキシ)-3,5,5-トリメチルシクロヘキサン、2,5-ジメチルヘキサン-2,5-ジヒドロキシパーオキシド、α,α´-ビス(第3ブチルパーオキシ)-p-ジイソプロピルベンゼン、2,5-ジメチル-2,5-ジ(ベンゾイルパーオキシ)ヘキサン、第3ブチルパーオキシイソプロピルカーボネート等が使用される。 The fluorine-containing elastomer obtained in this way has iodine or the like derived from a fluoroolefin iodide mixture that acts as a peroxide crosslinkable group in the copolymer, and is thus peroxide crosslinked by an organic peroxide. . Examples of the organic peroxide used for peroxide crosslinking include 2,5-dimethyl-2,5-bis (tertiary butylperoxy) hexane, 2,5-dimethyl-2,5-bis (tertiary butylperoxide). Oxy) hexyne-3, benzoyl peroxide, bis (2,4-dichlorobenzoyl) peroxide, dicumyl peroxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, tert-butyl peroxybenzene, 1,1 -Bis (tert-butylperoxy) -3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroxyperoxide, α, α'-bis (tert-butylperoxy) -p- Diisopropylbenzene, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tert-butylperoxyisopropyl carbonate and the like are used.

  これらの有機過酸化物が用いられるパーオキサイド架橋法では、通常共架橋剤として多官能性不飽和化合物、例えばトリ(メタ)アリルイソシアヌレート、トリ(メタ)アリルシアヌレート、トリアリルトリメリテート、N,N´-m-フェニレンビスマレイミド、ジアリルフタレート、トリス(ジアリルアミン)-s-トリアジン、亜リン酸トリアリル、1,2-ポリブタジエン、エチレングリコールジアクリレート、ジエチレングリコールジアクリレート等が、よりすぐれた加硫特性、機械的強度、圧縮永久歪特性などを得る目的で併用される。 In the peroxide crosslinking method in which these organic peroxides are used, polyfunctional unsaturated compounds such as tri (meth) allyl isocyanurate, tri (meth) allyl cyanurate, triallyl trimellitate, N, N´-m-phenylene bismaleimide, diallyl phthalate, tris (diallylamine) -s-triazine, triallyl phosphite, 1,2-polybutadiene, ethylene glycol diacrylate, diethylene glycol diacrylate, etc. Used for the purpose of obtaining characteristics, mechanical strength, compression set characteristics and the like.

  また、目的によっては、架橋助剤として2価金属の酸化物または水酸化物、例えばカルシウム、マグネシウム、鉛、亜鉛等の酸化物または水酸化物を用いることもできる。これらの化合物は、受酸剤としても作用する。 Depending on the purpose, an oxide or hydroxide of a divalent metal, for example, an oxide or hydroxide of calcium, magnesium, lead, zinc or the like can be used as a crosslinking aid. These compounds also act as acid acceptors.

  パーオキサイド架橋系に配合される以上の各成分は、一般に含フッ素エラストマー100重量部当り有機過酸化物が約0.1～10重量部、好ましくは約0.5～5重量部の割合で、共架橋剤が約0.1～10重量部、好ましくは約0.5～5重量部の割合で、また架橋助剤が約15重量部以下の割合でそれぞれ用いられ、含フッ素エラストマー組成物を形成する。組成物中には、上記各成分に加えて、従来公知の充填剤、補強剤、可塑剤、滑剤、加工助剤、顔料などを適宜配合することもできる。 Each of the above components to be blended in the peroxide crosslinking system generally contains about 0.1 to 10 parts by weight, preferably about 0.5 to 5 parts by weight of organic peroxide per 100 parts by weight of the fluorine-containing elastomer. About 0.1 to 10 parts by weight, preferably about 0.5 to 5 parts by weight, and a crosslinking aid is used in a ratio of about 15 parts by weight or less to form a fluorine-containing elastomer composition. In addition to the above-mentioned components, conventionally known fillers, reinforcing agents, plasticizers, lubricants, processing aids, pigments, and the like can be appropriately blended in the composition.

  パーオキサイド架橋は、前記各成分をロール混合、ニーダー混合、バンバリー混合、溶液混合など一般に用いられている混合法によって混合した後、加熱することによって行われる。加熱は、一般には約100～250℃で約1～120分間程度行われるプレス加硫および約150～300℃で0～30時間程度行われるオーブン加硫(二次加硫)によって行われる。 Peroxide crosslinking is performed by mixing the above components by a commonly used mixing method such as roll mixing, kneader mixing, Banbury mixing, solution mixing, and the like, followed by heating. The heating is generally performed by press vulcanization performed at about 100 to 250 ° C. for about 1 to 120 minutes and oven vulcanization (secondary vulcanization) performed at about 150 to 300 ° C. for about 0 to 30 hours.

　次に、実施例について本発明を説明する。 Next, the present invention will be described with reference to examples.

　参考例１
　攪拌機および温度計を備えた容量1200mlのオートクレーブに、
　　CF3(CF2)3(CH2CF2)(CF2CF2)2I (99GC％)
603g(0.99モル)およびジ第3ブチルパーオキサイド7g(0.05モル)を仕込み、真空ポンプでオートクレーブを脱気した。内温を80℃迄加熱したところで、エチレンを逐次的に導入し、内圧を0.5MPaとした。内圧が0.2MPa迄下がったら、再びエチレンを導入して0.5MPaとし、これをくり返した。内温を80～115℃に保ちながら、約3時間かけてエチレン41g(1.45モル)を導入した。内温50℃以下で内容物を回収し、
　　CF3(CF2)3(CH2CF2)(CF2CF2)2(CH2CH2)I (98GC％)
すなわち
　　C4F9CH2(CF2)5CH2CH2I
637g(収率98.8％)を得た。 Reference example 1
In an autoclave with a capacity of 1200 ml equipped with a stirrer and a thermometer,
CF 3 (CF 2 ) 3 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 I (99GC%)
603 g (0.99 mol) and 7 g (0.05 mol) of di-tert-butyl peroxide were charged, and the autoclave was deaerated with a vacuum pump. When the internal temperature was heated to 80 ° C., ethylene was sequentially introduced to adjust the internal pressure to 0.5 MPa. When the internal pressure decreased to 0.2 MPa, ethylene was introduced again to 0.5 MPa, and this was repeated. While maintaining the internal temperature at 80 to 115 ° C., 41 g (1.45 mol) of ethylene was introduced over about 3 hours. The contents are collected at an internal temperature of 50 ° C or less,
CF 3 (CF 2 ) 3 (CH 2 CF 2 ) (CF 2 CF 2 ) 2 (CH 2 CH 2 ) I (98GC%)
That is, C 4 F 9 CH 2 (CF 2 ) 5 CH 2 CH 2 I
637 g (98.8% yield) was obtained.

　実施例１
　冷却コンデンサ、熱電対およびマグネット攪拌子を備えた容量50mlのガラス製反応器に、上記参考例１で得られた3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-ノナデカフルオロ-1-ヨードドデカンC4F9CH2(CF2)5CH2CH2I 5g(7.8ミリモル)を含フッ素有機溶媒(旭硝子製品AK-225)15mlに溶解させた溶液として仕込み、氷冷した後、内温を0～10℃の範囲に保ちながら、1,8-ジアザビシクロ〔5.4.0〕-7-ウンデセン〔DBU〕2.6g(17.2ミリモル)を滴下した。滴下終了後、約0℃で約1時間攪拌し、次いで室温条件下で約23時間攪拌を継続した(全反応時間24時間)。 Example 1
The 3,3,4,4,5,5,6,6,7,7,9 obtained in Reference Example 1 was added to a 50 ml glass reactor equipped with a cooling condenser, thermocouple and magnet stirrer. , 9,10,10,11,11,12,12,12-nonadecafluoro-1-iodododecane C 4 F 9 CH 2 (CF 2 ) 5 CH 2 CH 2 I 5 g (7.8 mmol) A solution dissolved in 15 ml of a solvent (Asahi Glass product AK-225) was charged and cooled with ice. Then, while maintaining the internal temperature in the range of 0 to 10 ° C, 1,8-diazabicyclo [5.4.0] -7-undecene [ DBU] 2.6 g (17.2 mmol) was added dropwise. After completion of the dropwise addition, the mixture was stirred at about 0 ° C. for about 1 hour, and then stirred for about 23 hours at room temperature (total reaction time 24 hours).

　反応終了後、水20mlを用いた洗浄を2回、その後飽和食塩水による洗浄を1回行い、得られた反応生成物溶液を無水硫酸マグネシウムで脱水・乾燥させた。反応溶媒を減圧下で留去した後、残留物を減圧蒸留により精製し、蒸気温68～70℃/1kPaの留分を2.8g(収率77％)得た。得られた留分の構造を19F-NMRおよび1H-NMRで確認し、生成物Aと生成物Bとの重量比約48：52の混合物であることを確認した。
　　生成物A：3,3,4,4,5,5,6,6,7,7,9,10,10,11,11,12,12,12-オクタデカ
　　　　　　 フルオロドデカ-1,8-ジエン
　　　　　　 CF3CF2CF2CF=CHCF2CF2CF2CF2CF2CH=CH2
　　生成物B：3,3,4,4,5,5,6,6,7,9,9,10,10,11,11,12,12,12-オクタデカ
　　　　　　 フルオロドデカ-1,7-ジエン
　　　　　　 CF3CF2CF2CF2CH=CFCF2CF2CF2CF2CH=CH2
　　1H-NMR：TMS
　　　生成物Aδ=5.81(1H：-CF=CH-)、5.79(1H：-CF2-CH=)、5.97(2H：=CH 2)
　　　生成物Bδ=5.81(1H：-CH=CF-)、5.79(1H：-CF2-CH=)、5.97(2H：=CH 2)
　　19F-NMR：CFCl3
　　　生成物Aδ=-79.95(3F：CF 3-)、-108.35(2F：=CHCF 2-)、-111.34(1F：
　　　　　　　　-CF=)、-112.34(2F：-CF 2CH=)、-117.4～126.3(10F：-CF 2-)
　　　生成物Bδ=-80.20(3F：CF 3-)、-108.35(2F：=CHCF 2-)、-109.81(1F：
　　　　　　　　=CF-)、-112.34(2F：-CF 2CH=)、-117.4～126.3(10F：-CF 2-) After completion of the reaction, washing with 20 ml of water was performed twice and then with a saturated saline solution once, and the resulting reaction product solution was dehydrated and dried over anhydrous magnesium sulfate. After the reaction solvent was distilled off under reduced pressure, the residue was purified by distillation under reduced pressure to obtain 2.8 g (yield 77%) of a fraction having a vapor temperature of 68 to 70 ° C./1 kPa. The structure of the obtained fraction was confirmed by 19 F-NMR and 1 H-NMR, and it was confirmed that the mixture of the product A and the product B had a weight ratio of about 48:52.
Product A: 3,3,4,4,5,5,6,6,7,7,9,10,10,11,11,12,12,12-octadeca fluorododeca-1,8-diene CF 3 CF 2 CF 2 CF = CHCF 2 CF 2 CF 2 CF 2 CF 2 CH = CH 2
Product B: 3,3,4,4,5,5,6,6,7,9,9,10,10,11,11,12,12,12-octadeca fluorododeca-1,7-diene CF 3 CF 2 CF 2 CF 2 CH = CFCF 2 CF 2 CF 2 CF 2 CH = CH 2
1 H-NMR: TMS
Products Aδ = 5.81 (1H: -CF = C H- ), 5.79 (1H: -CF 2 -C H =), 5.97 (2H: = C H 2 )
Products Bδ = 5.81 (1H: -C H = CF-), 5.79 (1H: -CF 2 -C H =), 5.97 (2H: = C H 2 )
19 F-NMR: CFCl 3
Products Aδ = −79.95 (3F: C F 3 −), −108.35 (2F: = CHC F 2 −), −111.34 (1F:
-C F =), -112.34 (2F: -C F 2 CH =), -117.4-126.3 (10F: -C F 2- )
Product Bδ = -80.20 (3F: C F 3- ), -108.35 (2F: = CHC F 2- ), -109.81 (1F:
= C F- ), -112.34 (2F: -C F 2 CH =), -117.4-126.3 (10F: -C F 2- )

　実施例２
　実施例１において、DBUの使用量を1.3g(8.5ミリモル)に変更して反応させ、前記留分である生成物A-生成物B(重量比48：52)混合物1.2g(収率33％)および蒸気温76～77℃/1kPaの留分である下記生成物C 0.6g(純度98％、収率15％)を得た。
　　生成物C：3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-ノナデカ
　　　　　　 フルオロ-1-ドデセン
　　　　　　 CF3CF2CF2CF2CH2CF2CF2CF2CF2CF2CH=CH2
　　1H-NMRδ=2.90(2H：-CH 2-)、5.79(1H：-CF2-CH=)、5.97(2H：=CH 2)
　　19F-NMRδ=-82.02(3F：CF3-)、-113.04(4F：-CF 2CH2-)、-114.79(2F：
　　　　　　 -CF2CH=)、-121.9～-128.2(10F：-CF 2-) Example 2
In Example 1, the amount of DBU used was changed to 1.3 g (8.5 mmol) for the reaction, and 1.2 g (yield 33%) of the product A-product B (weight ratio 48:52) mixture as the fraction. And 0.6 g (purity 98%, yield 15%) of the following product C, which is a fraction having a steam temperature of 76 to 77 ° C./1 kPa.
Product C: 3,3,4,4,5,5,6,6,7,7,9,9,10,10,11,11,12,12,12-nonadeca fluoro-1-dodecene CF 3 CF 2 CF 2 CF 2 CH 2 CF 2 CF 2 CF 2 CF 2 CF 2 CH = CH 2
1 H-NMR δ = 2.90 (2H: -C H 2- ), 5.79 (1H: -CF 2 -C H =), 5.97 (2H: = C H 2 )
19 F-NMR δ = -82.02 (3F: CF 3- ), -113.04 (4F: -C F 2 CH 2- ), -114.79 (2F:
-CF 2 CH =), -121.9 to -128.2 (10F: -C F 2- )

　実施例３
　実施例１において、DBUの代りにトリエチルアミン1.8g(17.3ミリモル)を用い、全反応時間を48時間として反応させると、前記留分である生成物A-生成物B(重量比49：51)混合物2.0g(収率55％)および前記留分である生成物C 1.0g(収率26％)が得られた。 Example 3
In Example 1, 1.8 g (17.3 mmol) of triethylamine was used in place of DBU, and the reaction was carried out at a total reaction time of 48 hours. When the reaction was performed, the product A-product B (weight ratio 49:51) mixture as the fraction was obtained. 2.0 g (55% yield) and 1.0 g (26% yield) of the product C, the fraction, were obtained.

　実施例４
　実施例３において、溶媒を含フッ素有機溶媒からテトラヒドロフラン15mlに変更し、また反応温度を50℃、全反応時間を24時間に変更して反応させ、前記留分の生成物A-生成物B(重量比49：51)混合物2.7g(収率74％)を得た。 Example 4
In Example 3, the solvent was changed from a fluorine-containing organic solvent to 15 ml of tetrahydrofuran, the reaction temperature was changed to 50 ° C., the total reaction time was changed to 24 hours, and the product A-product B ( Weight ratio 49:51) 2.7 g (yield 74%) of the mixture was obtained.

　参考例２
　攪拌機および温度計を備えた容量1200mlのオートクレーブに、
　　CF3(CF2)3(CH2CF2)(CF2CF2)I (99GC％)
509g(0.99モル)およびジ第3ブチルパーオキサイド6.7g(0.05モル)を仕込み、真空ポンプでオートクレーブを脱気した。内温を80℃迄加熱したところで、エチレンを逐次的に導入し、内圧を0.5MPaとした。内圧が0.2MPa迄下がったら、再びエチレンを導入して0.5MPaとし、これをくり返した。内温を80～115℃に保ちながら、約3時間かけてエチレン38g(1.35モル)を導入した。内温50℃以下で内容物を回収し、
　　CF3(CF2)3(CH2CF2)(CF2CF2)(CH2CH2)I (98GC％)
すなわち
　　C4F9CH2(CF2)3CH2CH2I
530g(収率96％)を得た。 Reference example 2
In an autoclave with a capacity of 1200 ml equipped with a stirrer and a thermometer,
CF 3 (CF 2 ) 3 (CH 2 CF 2 ) (CF 2 CF 2 ) I (99GC%)
509 g (0.99 mol) and di-tert-butyl peroxide 6.7 g (0.05 mol) were charged, and the autoclave was deaerated with a vacuum pump. When the internal temperature was heated to 80 ° C., ethylene was sequentially introduced to adjust the internal pressure to 0.5 MPa. When the internal pressure decreased to 0.2 MPa, ethylene was introduced again to 0.5 MPa, and this was repeated. While maintaining the internal temperature at 80 to 115 ° C., 38 g (1.35 mol) of ethylene was introduced over about 3 hours. The contents are collected at an internal temperature of 50 ° C or less,
CF 3 (CF 2 ) 3 (CH 2 CF 2 ) (CF 2 CF 2 ) (CH 2 CH 2 ) I (98GC%)
That is, C 4 F 9 CH 2 (CF 2 ) 3 CH 2 CH 2 I
530 g (96% yield) was obtained.

　実施例５
　冷却コンデンサ、熱電対およびマグネット攪拌子を備えた容量50mlのガラス製反応器に、上記参考例２で得られた3,3,4,4,5,5,7,7,8,8,9,9,10,10,10-ペンタデカフルオロ-1-ヨードデカンC4F9CH2(CF2)3CH2CH2I 5g(9.3ミリモル)を含フッ素有機溶媒(旭硝子製品AK-225)15mlに溶解させた溶液として仕込み、氷冷した後、内温を0～10℃の範囲に保ちながら、1,8-ジアザビシクロ〔5.4.0〕-7-ウンデセン〔DBU〕3.0g(19.7ミリモル)を滴下した。滴下終了後、約0℃で約1時間攪拌し、次いで室温条件下で約23時間攪拌を継続した(全反応時間24時間)。 Example 5
To a 50 ml glass reactor equipped with a cooling condenser, thermocouple and magnet stirrer, 3,3,4,4,5,5,7,7,8,8,9 obtained in Reference Example 2 above. , 9,10,10,10-Pentadecafluoro-1-iododecane C 4 F 9 CH 2 (CF 2 ) 3 CH 2 CH 2 I 5 g (9.3 mmol) in fluorinated organic solvent (Asahi Glass Products AK-225) 15 ml After being cooled in ice and cooled with ice, 3.0 g (19.7 mmol) of 1,8-diazabicyclo [5.4.0] -7-undecene [DBU] was maintained while maintaining the internal temperature in the range of 0 to 10 ° C. It was dripped. After completion of the dropwise addition, the mixture was stirred at about 0 ° C. for about 1 hour, and then stirred for about 23 hours at room temperature (total reaction time 24 hours).

　反応終了後、水20mlを用いた洗浄を2回、その後飽和食塩水による洗浄を1回行い、得られた反応生成物溶液を無水硫酸マグネシウムで脱水・乾燥させた。反応溶媒を減圧下で留去した後、残留物を減圧蒸留により精製し、蒸気温53～55℃/1kPaの留分を2.5g(収率66％)得た。得られた留分の構造を19F-NMRおよび1H-NMRで確認し、生成物Dと生成物Eとの重量比約47：53の混合物であることを確認した。
　　生成物D：3,3,4,4,5,5,7,8,8,9,9,10,10,10-テトラデカフルオロデカ-
　　　　　　 1,6-ジエン
　　　　　　 CF3CF2CF2CF=CHCF2CF2CF2CH=CH2
　　生成物E：3,3,4,4,5,7,7,8,8,9,9,10,10,10-テトラデカフルオロデカ-
　　　　　　 1,5-ジエン
　　　　　　 CF3CF2CF2CF2CH=CFCF2CF2CH=CH2
　　1H-NMR：TMS
　　　生成物Dδ=5.81(1H：-CH=CF-)、5.79(1H：-CF2-CH=)、5.97(2H：=CH 2)
　　　生成物Eδ=5.82(1H：-CH=CF-)、5.79(1H：-CF2-CH=)、5.97(2H：=CH 2)
　　19F-NMR：CFCl3
　　　生成物Dδ=-80.23(3F：CF 3-)、-107.80(2F：=CHCF 2-)、-111.34(1F：
　　　　　　　　-CF=)、-112.42(2F：-CF 2CH=)、-116.7～128.2(6F：-CF 2-)
　　　生成物Eδ=-79.97(3F：CF 3-)、-108.35(2F：=CHCF 2-)、-111.34(1F：
　　　　　　　　=CF-)、-112.42(2F：-CF 2CH=)、-116.7～128.2(6F：-CF 2-) After completion of the reaction, washing with 20 ml of water was performed twice and then with a saturated saline solution once, and the resulting reaction product solution was dehydrated and dried over anhydrous magnesium sulfate. After the reaction solvent was distilled off under reduced pressure, the residue was purified by distillation under reduced pressure to obtain 2.5 g (yield 66%) of a fraction having a vapor temperature of 53 to 55 ° C./1 kPa. The structure of the obtained fraction was confirmed by 19 F-NMR and 1 H-NMR, and it was confirmed that the mixture of the product D and the product E had a weight ratio of about 47:53.
Product D: 3,3,4,4,5,5,7,8,8,9,9,10,10,10-tetradecafluorodeca-
1,6-diene CF 3 CF 2 CF 2 CF = CHCF 2 CF 2 CF 2 CH = CH 2
Product E: 3,3,4,4,5,7,7,8,8,9,9,10,10,10-tetradecafluorodeca-
1,5-diene CF 3 CF 2 CF 2 CF 2 CH = CFCF 2 CF 2 CH = CH 2
1 H-NMR: TMS
Products Dδ = 5.81 (1H: -C H = CF-), 5.79 (1H: -CF 2 -C H =), 5.97 (2H: = C H 2 )
Products Eδ = 5.82 (1H: -C H = CF-), 5.79 (1H: -CF 2 -C H =), 5.97 (2H: = C H 2 )
19 F-NMR: CFCl 3
Product Dδ = -80.23 (3F: C F 3- ), -107.80 (2F: = CHC F 2- ), -111.34 (1F:
-C F =), -112.42 (2F: -C F 2 CH =), -116.7-128.2 (6F: -C F 2- )
Product Eδ = −79.97 (3F: C F 3 −), −108.35 (2F: = CHC F 2 −), −111.34 (1F:
= C F- ), -112.42 (2F: -C F 2 CH =), -116.7-128.2 (6F: -C F 2- )

　実施例６
　(1) 攪拌機を備えた容量30Lのステンレス鋼製反応器を真空にした後、
　　　　水　　　　　　　　　　　　　　　　　　　　 13kg
　　　　C7F15COONH4　　　　　　　　　　　　　　　　　39g
　　　　Na2HPO4・12H2O　 　　　　　　　　　　　　　　26g
　　　　CBr2=CHF　　　　 　　　　　　　　　　　　　 26g
　　　　ICF2CF2Br　　　　　　　　　　　　　　　　　 24g
　　　　実施例５で得られたジエン混合物　　　　　　 45g
　　　　　　C3F7CF=CHCF2CF2CF2CH=CH2 (47モル％)
　　　　　　C4F9CH=CFCF2CF2CH=CH2　　(53モル％)
を仕込み、その後
　　　　テトラフルオロエチレン〔TFE〕　　　　　　　490g (13モル％)
　　　　フッ化ビニリデン〔VdF〕　　　　　　　　　 1180g (47モル％)
　　　　ヘキサフルオロプロピレン〔HFP〕　　　　　 2330g (40モル％)
を仕込み、70℃に昇温した。昇温後の圧力は、3.88MPa・Gであった。なお、ジエン混合物は、重合反応開始時および分添混合ガスの分添工程中に計20回に分けて添加した。 Example 6
(1) After vacuuming a 30L stainless steel reactor equipped with a stirrer,
Water 13kg
C 7 F 15 COONH 4 39g
Na 2 HPO 4・ 12H 2 O 26g
CBr 2 = CHF 26g
ICF 2 CF 2 Br 24g
45 g of the diene mixture obtained in Example 5
C 3 F 7 CF = CHCF 2 CF 2 CF 2 CH = CH 2 (47 mol%)
C 4 F 9 CH = CFCF 2 CF 2 CH = CH 2 (53 mol%)
And then 490 g of tetrafluoroethylene [TFE] (13 mol%)
Vinylidene fluoride [VdF] 1180 g (47 mol%)
Hexafluoropropylene [HFP] 2330g (40mol%)
The temperature was raised to 70 ° C. The pressure after the temperature increase was 3.88 MPa · G. The diene mixture was added in a total of 20 times at the start of the polymerization reaction and during the addition step of the added mixed gas.

　次いで、過硫酸アンモニウム24gを水500g中に溶解させた重合開始剤水溶液を反応器中に圧入し、重合反応を開始させた。重合反応の進行に伴って、反応器内の圧力が減少するため、圧力を3.75～3.85MPa・Gを維持するように、TFE/VdF/HFP(モル百分率16.4/62.2/21.4)混合ガスを反応器中に分添し、分添混合ガス量が合計10.2kgとなった時点で分添を止め(反応開始後約10時間)、約30～50分間のエージングを行った。そのときの反応器中の圧力は、1.8MPa・Gであった。 Next, a polymerization initiator aqueous solution in which 24 g of ammonium persulfate was dissolved in 500 g of water was pressed into the reactor to initiate the polymerization reaction. As the polymerization reaction proceeds, the pressure in the reactor decreases, so the TFE / VdF / HFP (molar percentage 16.4 / 62.2 / 21.4) gas mixture is reacted so that the pressure is maintained at 3.75 to 3.85 MPa · G. When the total amount of the mixed gas was 10.2 kg, the addition was stopped (about 10 hours after the start of the reaction), and aging was performed for about 30 to 50 minutes. The pressure in the reactor at that time was 1.8 MPa · G.

　反応終了後、反応混合物を反応器中から取り出し、塩化カルシウム水溶液を用いて凝析することによって、含フッ素エラストマーAを得た。得られた含フッ素エラストマーAの共重合組成をNMR分析法によって測定すると、VdF/TFE/HFP(モル百分率67.1/16.0/16.9)共重合体であった。 After completion of the reaction, the reaction mixture was taken out of the reactor and coagulated with an aqueous calcium chloride solution to obtain fluorinated elastomer A. When the copolymer composition of the obtained fluorinated elastomer A was measured by NMR analysis, it was a VdF / TFE / HFP (molar percentage 67.1 / 16.0 / 16.9) copolymer.

　(2) 上記含フッ素エラストマーA 　　　　　　　　　　　　100重量部
　　　MTカーボンブラック　　　　　　　　　　　　　　　　 20　〃　
　　　酸化亜鉛　　　　　　　　　　　　　　　　　　　　　　5　〃　
　　　トリアリルイソシアヌレート(日本化成製品TAIC M60)　　5　〃　
　　　有機過酸化物(日本油脂製品パーヘキサ25B40)　　　　 3.5　〃　
を、オープンロールを用いて混練し、混合物を180℃で10分間プレス加硫し、次いで230℃で22時間オーブン加硫(二次加硫)した。加硫物について、硬度(ISO 48に対応するJIS K6253準拠)、引張特性(ISO 37に対応するJIS K6251準拠)および圧縮永久歪(ASTM Method-B/P-24 Oリング；200℃、70時間)をそれぞれ測定した。 (2) Fluoroelastomer A 100 parts by weight MT Carbon Black 20 上 記
Zinc oxide 5 〃
Triallyl isocyanurate (Nippon Kasei products TAIC M60) 5 〃
Organic peroxides (NIPPON OIL & PRODUCTS PERHEXA 25B40) 3.5 〃
Was kneaded using an open roll, and the mixture was press vulcanized at 180 ° C. for 10 minutes, and then oven vulcanized (secondary vulcanization) at 230 ° C. for 22 hours. For vulcanized products, hardness (conforms to JIS K6253 corresponding to ISO 48), tensile properties (conforms to JIS K6251 corresponding to ISO 37) and compression set (ASTM Method-B / P-24 O-ring; 200 ° C, 70 hours) ) Were measured respectively.

　実施例７
　(1) 攪拌機を備えた容量30Lのステンレス鋼製反応器を真空にした後、
　　　　水　　　　　　　　　　　　　　　　　　　　15.5kg
　　　　C7F15COONH4　　　　　　　　　　　　　　　　　71g
　　　　Na2HPO4・12H2O　　　　　　　　　　　　　　　 51g
　　　　ICF2CF2CF2CF2I　　　　　　　　　　　　　　　 45g
　　　　実施例５で得られたジエン混合物　　　　　　 45g
　　　　　　C3F7CF=CHCF2CF2CF2CH=CH2 (47モル％)
　　　　　　C4F9CH=CFCF2CF2CH=CH2　　(53モル％)
を仕込み、その後
　　　　テトラフルオロエチレン〔TFE〕　　　　　　　210g (8モル％)
　　　　フッ化ビニリデン〔VdF〕　　　　　　　　　 1140g (70モル％)
　　　　パーフルオロ(メチルビニルエーテル)〔FMVE〕 930g (22モル％)
を仕込み、80℃に昇温した。昇温後の圧力は、3.11MPa・Gであった。なお、ジエン混合物は、重合反応開始時および分添混合ガスの分添工程中に計20回に分けて添加した。 Example 7
(1) After vacuuming a 30L stainless steel reactor equipped with a stirrer,
15.5 kg of water
C 7 F 15 COONH 4 71g
Na 2 HPO 4・ 12H 2 O 51g
ICF 2 CF 2 CF 2 CF 2 I 45g
45 g of the diene mixture obtained in Example 5
C 3 F 7 CF = CHCF 2 CF 2 CF 2 CH = CH 2 (47 mol%)
C 4 F 9 CH = CFCF 2 CF 2 CH = CH 2 (53 mol%)
And then tetrafluoroethylene [TFE] 210g (8mol%)
Vinylidene fluoride [VdF] 1140g (70mol%)
Perfluoro (methyl vinyl ether) [FMVE] 930 g (22 mol%)
The temperature was raised to 80 ° C. The pressure after the temperature increase was 3.11 MPa · G. The diene mixture was added in a total of 20 times at the start of the polymerization reaction and during the addition step of the added mixed gas.

　次いで、過硫酸アンモニウム0.8gを水500g中に溶解させた重合開始剤水溶液を反応器中に圧入し、重合反応を開始させた。重合反応の進行に伴って、反応器内の圧力が減少するため、圧力を3.0～2.9MPa・Gを維持するように、TFE/VdF/FMVE(モル百分率9.0/73.0/18.0)混合ガスを反応器中に分添し、分添混合ガス量が合計7.2kgとなった時点で分添を止め(反応開始後約4時間)、約120分間のエージングを行った。そのときの反応器中の圧力は、1.2MPa・Gであった。 Next, an aqueous polymerization initiator solution in which 0.8 g of ammonium persulfate was dissolved in 500 g of water was injected into the reactor to initiate the polymerization reaction. As the polymerization reaction proceeds, the pressure in the reactor decreases, so the TFE / VdF / FMVE (molar percentage 9.0 / 73.0 / 18.0) mixed gas is reacted so that the pressure is maintained at 3.0 to 2.9 MPa · G. When the total amount of the mixed gas reached 7.2 kg, the addition was stopped (about 4 hours after the start of the reaction), and aging was performed for about 120 minutes. The pressure in the reactor at that time was 1.2 MPa · G.

　反応終了後、反応混合物を反応器中から取り出し、塩化カルシウム水溶液を用いて凝析することによって、含フッ素エラストマーBを得た。得られた含フッ素エラストマーBの共重合組成をNMR分析法によって測定すると、VdF/TFE/FMVE(モル百分率72.8/9.0/18.2)共重合体であった。 After completion of the reaction, the reaction mixture was taken out from the reactor and coagulated with an aqueous calcium chloride solution to obtain fluorinated elastomer B. When the copolymer composition of the obtained fluorinated elastomer B was measured by NMR analysis, it was a VdF / TFE / FMVE (molar percentage 72.8 / 9.0 / 18.2) copolymer.

　(2) 上記含フッ素エラストマーB 　　　　　　　　　　　　100重量部
　　　MTカーボンブラック　　　　　　　　　　　　　　　　 30　〃　
　　　酸化亜鉛　　　　　　　　　　　　　　　　　　　　　　6　〃　
　　　トリアリルイソシアヌレート(日本化成製品TAIC M60)　6.7　〃　
　　　有機過酸化物(日本油脂製品パーヘキサ25B40)　　　　 1.3　〃　
を、オープンロールを用いて混練し、混合物を180℃で10分間プレス加硫し、次いで220℃で22時間オーブン加硫(二次加硫)した。加硫物について、硬度、引張特性および圧縮永久歪をそれぞれ測定した。 (2) 100 parts by weight of the above fluorine-containing elastomer B MT carbon black 30 〃
Zinc oxide 6 〃
Triallyl isocyanurate (Nippon Kasei products TAIC M60) 6.7 〃
Organic peroxides (NIPPON OIL & PRODUCTS PERHEXA 25B40) 1.3 〃
Was kneaded using an open roll, and the mixture was press vulcanized at 180 ° C. for 10 minutes, and then oven vulcanized (secondary vulcanization) at 220 ° C. for 22 hours. The vulcanizate was measured for hardness, tensile properties and compression set.

　比較例１
　実施例１において、ジエン混合物が共重合反応に用いられなかった。得られた含フッ素エラストマーCの共重合組成は、VdF/TFE/HFP(モル百分率67.0/16.0/17.0)共重合体であった。この含フッ素エラストマーCを用いての加硫も、実施例６と同様に行われた。 Comparative Example 1
In Example 1, the diene mixture was not used for the copolymerization reaction. The copolymer composition of the obtained fluorinated elastomer C was a VdF / TFE / HFP (molar percentage 67.0 / 16.0 / 17.0) copolymer. Vulcanization using this fluorine-containing elastomer C was also carried out in the same manner as in Example 6.

　比較例２
　実施例７において、ジエン混合物の代りに、
　　　　CF2=CFOCF2CF2OCF=CF2　　　　　　　　　　　　　　34g
が用いられた。得られた含フッ素エラストマーDの共重合組成は、VdF/TFE/FMVE(モル百分率73.2/9.0/17.8)共重合体であった。この含フッ素エラストマーDを用いての加硫も、実施例７と同様に行われた。 Comparative Example 2
In Example 7, instead of the diene mixture,
CF 2 = CFOCF 2 CF 2 OCF = CF 2 34g
Was used. The copolymer composition of the obtained fluorine-containing elastomer D was a VdF / TFE / FMVE (molar percentage 73.2 / 9.0 / 17.8) copolymer. Vulcanization using this fluorine-containing elastomer D was also carried out in the same manner as in Example 7.

　比較例３
　実施例７において、ジエン混合物が共重合反応に用いられなかった。得られた含フッ素エラストマーEの共重合組成は、VdF/TFE/FMVE(モル百分率73.0/9.0/18.0)共重合体であった。この含フッ素エラストマーEを用いての加硫も、実施例７と同様に行われた。 Comparative Example 3
In Example 7, the diene mixture was not used for the copolymerization reaction. The copolymer composition of the obtained fluorinated elastomer E was a VdF / TFE / FMVE (molar percentage 73.0 / 9.0 / 18.0) copolymer. Vulcanization using this fluorine-containing elastomer E was also carried out in the same manner as in Example 7.

　以上の実施例６～７および比較例１～３で測定された結果は、次の表に示される。

Figure JPOXMLDOC01-appb-I000001
The results measured in Examples 6 to 7 and Comparative Examples 1 to 3 are shown in the following table.
Figure JPOXMLDOC01-appb-I000001

Claims (12)

　一般式
　　　CF3(CF2)nCF=CH(CF2)m+1CH=CH2　　　　　　　　　　　　〔Ia〕
および一般式
　　　CF3(CF2)n+1CH=CF(CF2)mCH=CH2　　　　　　　　　　　　〔Ib〕
(ここで、nは0～5の整数であり、mは0～6の整数である)で表わされるポリフルオロアルカジエン混合物。 General formula CF 3 (CF 2 ) n CF = CH (CF 2 ) m + 1 CH = CH 2 (Ia)
And the general formula CF 3 (CF 2 ) n + 1 CH = CF (CF 2 ) m CH = CH 2 (Ib)
(Where n is an integer from 0 to 5 and m is an integer from 0 to 6). 　一般式
　　　CF3(CF2)n+1CH2(CF2)m+1(CH2CH2)I　　　　　　　　　　　 〔II〕
(ここで、nは0～5の整数であり、mは0～6の整数である)で表わされるポリフルオロアルキルアイオダイドに有機塩基性化合物を反応させ、生成物〔Ia〕および〔Ib〕の混合物留分として取得することを特徴とする請求項１記載のポリフルオロアルカジエン混合物の製造法。 General formula CF 3 (CF 2 ) n + 1 CH 2 (CF 2 ) m + 1 (CH 2 CH 2 ) I (II)
(Where n is an integer of 0 to 5 and m is an integer of 0 to 6) is reacted with an organic basic compound, and the products [Ia] and [Ib] The method for producing a polyfluoroalkadiene mixture according to claim 1, wherein the mixture is obtained as a mixture fraction. 　有機塩基性化合物がポリフルオロアルキルアイオダイドに対し1.95～2.5のモル比で用いられた請求項２記載のポリフルオロアルカジエン混合物の製造法。 The method for producing a polyfluoroalkadiene mixture according to claim 2, wherein the organic basic compound is used in a molar ratio of 1.95 to 2.5 with respect to the polyfluoroalkyl iodide. 　有機塩基性化合物が含窒素有機塩基性化合物である請求項２記載のポリフルオロアルカジエン混合物の製造法。 The method for producing a polyfluoroalkadiene mixture according to claim 2, wherein the organic basic compound is a nitrogen-containing organic basic compound. 　含窒素有機塩基性化合物が1,8-ジアザビシクロ〔5.4.0〕-7-ウンデセンである請求項４記載のポリフルオロアルカジエン混合物の製造法。 The process for producing a polyfluoroalkadiene mixture according to claim 4, wherein the nitrogen-containing organic basic compound is 1,8-diazabicyclo [5.4.0] -7-undecene. 　含フッ素有機溶媒中で反応が行われる請求項４記載のポリフルオロアルカジエン混合物の製造法。 The process for producing a polyfluoroalkadiene mixture according to claim 4, wherein the reaction is carried out in a fluorine-containing organic solvent. 　含窒素有機塩基性化合物がトリエチルアミンである請求項４記載のポリフルオロアルカジエン混合物の製造法。 The method for producing a polyfluoroalkadiene mixture according to claim 4, wherein the nitrogen-containing organic basic compound is triethylamine. 　テトラヒドロフラン溶媒中で反応が行われる請求項７記載のポリフルオロアルカジエン混合物の製造法。 The process for producing a polyfluoroalkadiene mixture according to claim 7, wherein the reaction is carried out in a tetrahydrofuran solvent. 　含フッ素エラストマーの共重合性単量体として用いられる請求項１記載のポリフルオロアルカジエン混合物。 The polyfluoroalkadiene mixture according to claim 1, which is used as a copolymerizable monomer for a fluorine-containing elastomer. 　請求項９記載のポリフルオロアルカジエン混合物を共重合性単量体としてフッ素化オレフィン単量体と共重合反応させた含フッ素共重合体であるパーオキサイド架橋可能な含フッ素エラストマー。 A peroxide-crosslinkable fluorine-containing elastomer which is a fluorine-containing copolymer obtained by copolymerizing the polyfluoroalkadiene mixture according to claim 9 with a fluorinated olefin monomer as a copolymerizable monomer. 　ポリフルオロアルカジエン混合物を共重合させた含フッ素共重合体がフッ化ビニリデン-テトラフルオロエチレン系共重合体である請求項１０記載のパーオキサイド架橋可能な含フッ素エラストマー。 The peroxide-crosslinkable fluorine-containing elastomer according to claim 10, wherein the fluorine-containing copolymer obtained by copolymerizing a polyfluoroalkadiene mixture is a vinylidene fluoride-tetrafluoroethylene copolymer. 　フッ化ビニリデン-テトラフルオロエチレン系共重合体がフッ化ビニリデン-テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体またはフッ化ビニリデン-テトラフルオロエチレン-パーフルオロ(低級アルキルビニルエーテル)共重合体である請求項１１記載のパーオキサイド架橋可能な含フッ素エラストマー。 12. The vinylidene fluoride-tetrafluoroethylene copolymer is a vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer or a vinylidene fluoride-tetrafluoroethylene-perfluoro (lower alkyl vinyl ether) copolymer. The peroxide crosslinkable fluorine-containing elastomer described.
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CA2723453A1 (en) 2009-12-17
US8163857B2 (en) 2012-04-24
CN102066296B (en) 2014-11-26
JPWO2009151109A1 (en) 2011-11-17
US20110077371A1 (en) 2011-03-31
EP2284145B1 (en) 2013-09-11
EP2284145A4 (en) 2013-01-09
CA2723453C (en) 2012-12-04
CN102066296A (en) 2011-05-18
EP2284145A1 (en) 2011-02-16

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